He played his last ATP match in 2018, and is coaching fellow collegiate player Dominik Koepfer, and Zachary Svajda.

He trained at the USTA headquarter in Boca Raton and shared an apartment with his best friend and former vol teammate, Tennys Sandgren.

He also has a multi-year deal with ABN AMRO Clearing and writes a weekly blog documenting his progress on their website.

Rhyne was coached by his grandfather, but he went on to train under the USTA Player's Development Program after winning the Junior Orange Bowl 14s.

Junior Achievements in Singles 2008 US Open Junior Tennis Championships Quarterfinalist 2007 Easter Bowl Champion 2007 USTA International Spring Championships Finalist 2006 Jerry Simmons ITF Junior Circuit – South Carolina Champion Junior Achievements in Doubles 2007 Yucatán World Cup Doubles Champion with Ričardas Berankis 2007 USTA International Spring Championships Finalist with Ryan Lipman 2006 Jerry Simmons ITF Junior Circuit – College Station, Texas Champion with Devin Britton 2006 Costa Rica Bowl Champion with Blake Davis 2005 Chanda Rubin American Junior Tennis Classic – Georgia Finalist with Devin Britton Rhyne won the USA F16 in Pittsburgh in 2007 at the age of 16 years and 3 months, which made him the youngest U.S. male to win an ITF Men's Circuit event in the United States (however, stats for this are held since 1998).

Since claiming his 1st futures title in 2007, Williams couldn't handle the pressure of turning pro and decided to go to college, "I guess the main reason I went to school was to mature," he recalls.

His grandfather, Mike DePalmer Sr., is the most successful head coach in Volunteer history[citation needed], and his mother and uncle were both All-Americans in Knoxville.

He started out his career with a splash, earning 2010 Southeastern Conference Freshman of the Year honors and helping the team to the NCAA finals.

He defeated Steve Johnson of the University of Southern California in the finals of the 2010 USTA/ITA National Intercollegiate Indoor Championships to become the third Tennessee player in program history to win the event.

1 and 2 singles positions during the team season and played doubles with fellow Tennessee native Tennys Sandgren.

He concluded his college career by reaching the final of the 2011 NCAA Singles Championship, this time losing to Johnson in three sets.

Williams gained 100 points and had defeated Austin Krajicek, Rajeev Ram, Alex Kuznetsov, and Frank Dancevic on his way to the finals.

In the same tournament for doubles, Williams partnered once again with Sandgren, and they reached the finals before once again losing a third-set super-tie breaker.

Williams made his first career ATP semifinal at the U.S. Men's Clay Court Championships in Houston, defeating Pella Guido, Ivo Karolvic, and Ruben Ramirez Hidalgo before falling to World No.

Williams made his first ATP Doubles Final partnering Tim Smyczek at Hall of Fame Tennis Championships.

Williams struggled with shoulder injury and didn't fare well in the USO summer hardcourt swing.