He broke a half-dozen school passing marks, was ACC Rookie of the Week a record eight times, and earned honors as the conference Freshman of the Year.

Once again, Rivers delivered an MVP performance in the most important game of the year, pacing the Wolfpack to a dominating 28–6 win over Notre Dame.

However, despite Rivers' record of success in college and high accuracy (72 completion percentage for his senior season), questions about his lack of arm strength and his unorthodox side-arm throwing motion were concerns for some NFL general managers.

[38] All three would enjoy lengthy and successful careers with the teams that signed them and have been compared favorably to the 1983 NFL draft, which included Hall of Fame quarterbacks John Elway, Jim Kelly, and Dan Marino.

[40] However, due to a protracted contract negotiation with the San Diego Chargers, Rivers only reported to the team during the last week of training camp, and incumbent Drew Brees retained his starting job.

He only threw passes in the second half of the last game of the 2004 season, a victory over the Kansas City Chiefs, by which time the Chargers had already clinched a home playoff spot and the AFC West division title.

Expectations were high for Rivers due to the large amount of talent on the Chargers' offense and the performance of his peers from the 2004 draft (Eli Manning and Ben Roethlisberger) as starters.

Football Outsiders projected that Rivers would become an NFL star before the 2006 season due to his spectacular completion percentage in college (72% as a senior).

[50] The fifth week of the season, the reigning Super Bowl champion Pittsburgh Steelers came to town, and Bill Cowher's defensive game plan revolved around stopping running back LaDainian Tomlinson.

This game marked a turning point for Rivers, who, aided by head coach Marty Schottenheimer's opening of the playbook, led the team in a come-from-behind victory, throwing 24-of-37 for 242 yards and two touchdowns, winning 23–13.

San Diego outscored Cincinnati 42–13 in the second half, winning the game 49–41, matching the largest comeback in franchise history from 23 years before for the Chargers.

[74] On January 3, 2009, in the Wild Card Round, the San Diego Chargers defeated the Indianapolis Colts to advance to the AFC Divisional Playoff.

He set up Nate Kaeding for a game-tying field goal that would lead to overtime, where the Chargers would go on to win 23–17, thanks to a Darren Sproles touchdown.

In the Divisional Round 35–24 loss to the Pittsburgh Steelers, Rivers played well, throwing for over 300 yards and three touchdowns, but was sacked four times and threw an interception.

[82] The Chargers started off the year slowly again at 3–5 and finished a disappointing 9–7 and their four-year reign as AFC West champions ended while they missed the playoffs.

[88][89] Rivers threw for four passing touchdowns, two to backup tight end Randy McMichael and the other two to rookie receiver Seyi Ajirotutu in a comeback 29–23 victory over the Houston Texans.

[129] In their Week 4 win over the Dallas Cowboys, Rivers set an NFL record for completion percentage (83%) for a quarterback who also threw for over 400 yards (401), three touchdowns, and one interception.

In Week 17, against the Kansas City Chiefs, Rivers led a fourth quarter and overtime comeback to win the game, and clinch the 6th seed in the AFC playoffs.

[128] With the Chargers having a capable running attack, an adjusted offensive line, and an improved defense, Rivers was not pressured to force his throws, and he led all quarterbacks in the league with a 49.4 third-down conversion rate when passing.

After the game, Rivers and several other Chargers players returned to the field to sign autographs for the fans, as they were unsure if it would be the team's final time playing in San Diego.

[176] In that game, he completed 28 of 37 passes for 387 yards and three touchdowns in a 30–10 win over the Raiders, earning him his second AFC Offensive Player of the Week of the season.

[185] After a 35–23 loss to the Los Angeles Rams in Week 3, Rivers helped lead the Chargers to a four-game winning streak where he threw for over 300 yards twice and had nine passing touchdowns to two interceptions.

[201] In a low-scoring duel with the Lions in Week 2, Rivers had a chance to lead the Chargers on a game-winning touchdown drive but threw a late interception near the redzone.

[202] In Week 3, down 7 late in the fourth quarter, Rivers drove deep into Texans' territory with five pass completions but was unable to reach the endzone in the loss.

[221] During the game against the Green Bay Packers in Week 11, Rivers ruptured his plantar plate, which was later reported to require offseason surgery, though he would play through the remainder of the season with the injury.

[224] Rivers recorded his 12th season with at least 4,000 passing yards, tying him with Tom Brady and Drew Brees at the time for second-most in NFL history.

"[227] He announced his intention to retire with the Chargers,[228] and reaffirmed his plans to become the head coach of the St. Michael Catholic High School football team in Fairhope, Alabama.

[249] In 2011, he was named one of three finalists for the Walter Payton NFL Man of the Year Award for his work with the Rivers of Hope Foundation, an endeavor he and his wife oversaw from 2010 to 2012 to help foster children.

[254] Rivers received an honorary degree, doctor of humane letters, and addressed the class of 2014 at the 125th annual commencement ceremony of the Catholic University of America (CUA) on May 17, 2014.

[256] On August 26, 2021, Rivers won his first game as a high school football head coach, leading the St. Michael Catholic Cardinals to a 49–0 victory.