In 2012, he played for Al-Nasr Dubai SC, in the UAE Arabian Gulf League, but returned to Fiorentina for a season later that year.

He then moved to Brescia, playing for two seasons under manager Carlo Mazzone, alongside Roberto Baggio and Pep Guardiola.

He consequently gained his first cap for the Italy national team in a friendly match 18 August 2004 lost 2–0 to Iceland in Reykjavík, which also marked Marcello Lippi's debut at the helm of the Azzurri.

[6] In the following season, Toni confirmed his prolificity by scoring 20 goals in Palermo's first Serie A campaign, leading the Sicilian club to a historical first qualification to the UEFA Cup.

Toni expressed his desire to leave the team several times during the summer to the press, but was eventually convinced by club President Andrea Della Valle to stay.

On 30 May 2007, Bayern Munich chairman Karl-Heinz Rummenigge confirmed that Toni had signed a four-year contract with the club after agreeing to a deal worth €11.58 million with Fiorentina.

[14] Toni battled an Achilles tendon injury for most of the second half of the 2008–09 season, but still finished as Bayern's leading scorer in league play, tallying 14 goals in 25 Bundesliga appearances.

On 31 December 2009, Bayern Munich confirmed the transfer of the Italian striker on a six-month loan basis to Roma,[18][19][20] which offered him pre-tax basic salary of €3.1 million.

Toni would go on to score five goals in total for the Giallorossi during the remainder of the 2009–10 season, including the winner against Internazionale[22] to cut the Milanese club's lead in Serie A to a single point ahead of Roma.

[26] On 31 August 2012, in the closing hour of the transfer market, Fiorentina announced that they completed the signing of Luca Toni, after he had been previously linked with a move to Siena.

Toni made it a goal-scoring return for La Viola when, after coming on as a 64th-minute substitute for Adem Ljajić, he scored with his first touch the second goal in a 2–0 win over Catania in the Stadio Artemio Franchi on 16 September 2012.

[29] In his Serie A debut for the club on 24 August, Toni scored twice as Verona recorded a 2–1 home win over Milan on the opening day of the season.

[45] He scored his first international goal on 4 September 2004, after coming off the bench in a 2–1 home win against Norway, in a World Cup Qualifying match.

[47][48] On 11 June 2005, he captained the Italian squad for the first time in his career in a friendly match in New York against Ecuador, due to the absence of Fabio Cannavaro and other experienced players; he scored Italy's only goal in the eventual 1–1 draw.

[49][50] On 7 September, Toni scored his first international hat-trick in a 4–1 victory against Belarus in a 2006 World Cup qualifying match, becoming the first Fiorentina player ever to do so.

[61] After undergoing surgery due to an injury to his left foot which he had struggled to overcome since the beginning of the 2006–07 season, he missed Italy's next two qualifiers against the Faroe Islands and Lithuania.

[62][63] He returned to action for his nation's qualification game against Georgia in Genoa on 13 October, and assisted Fabio Grosso, who scored Italy's second goal in a 2–0 win.

[64] On 17 November 2007, Toni struck in the first minute of a 2–1 win in a qualifying match against Scotland at Hampden Park, which secured Italy's place at the final stages of the competition.

[70] Toni's main contribution for the team was winning a decisive penalty kick in the final group match against France, which ended 2–0, and allowed the Italians to progress to the knock-out round.

[72] Despite disappointing at Euro 2008, Toni was called up by returning coach Marcello Lippi for Italy's first two 2010 FIFA World Cup qualifiers.

[79] Toni's goalscoring form with Verona in 2014 saw him become a popular potential candidate for a place as a reserve in Italy's 23-man 2014 FIFA World Cup squad,[80] although he was later excluded from Cesare Prandelli's final team for the tournament.

[95] A prolific goal-scorer,[96] Toni was a traditional centre-forward,[97] who excelled in the air and acrobatically; although in his youth he was known for his attacking movement, which allowed him to play anywhere along the front-line or off of his teammates, he mainly operated in the penalty area in his later career, as he lost his pace and his work-rate decreased.

[100] Although his physical, opportunistic, "goal-poaching" style of play was at times criticized as unrefined and unorthodox, due to his lack of notable technical skills, he also drew praise throughout his career for his leadership and ability to utilise his height, solid first touch, and strong physique to win aerial challenges, hold up the ball for his teammates, and provide them with assists when playing with his back to goal, in addition to his ability to score goals himself.

[96][98][101] Writing for The Guardian, Tom Mason has said of his play, "His retirement marks the end of not only a remarkable career, but of a whole breed of striker...he seems to be a relic of an out-dated and discredited ideology.

In a world where forwards are the first line of defense, where high-intensity pressing and sharp bursts of energy are a prerequisite for strikers, there seems to be little room for players in the mold of Luca Toni.

[110] In 2019, he stated that he has center-right political views and that he is a supporter of anti-illegal immigrant politician Matteo Salvini, joining him on stage during a rally in Modena.