Tolliver committed to Creighton in the fall of 2002. He was one of four players from his Kickapoo High School team to play Division Ibasketball; the team ended his senior season of 2002–03 ranked 12th by the USA Today and as the Missouri Class 5A State Champions. At Creighton, Tolliver played in a reserve role during his freshman season behind veterans Brody Deren, Mike Grimes, and Joe Dabbert, but saw action in 27 games. He started 30 of Creighton's 34 games his sophomore season, including an 8-point, 7-rebound performance in a 75-57 victory over Missouri State in the 2005 MVC tournament championship game. Tolliver earned second-team all-MVC honors during his junior season and had a memorable last-second shot to win a game against Wichita State on January 28, 2006. Tolliver was named first-team all MVC, a finalist for the Lowe's Senior CLASS award, and to the Collegeinsider.com mid-major All-America team during his senior year, and helped Creighton return to the NCAA Tournament and a 22-11 record. Tolliver started all 33 of the team's games and broke the 1,000 point mark for his career in his final collegiate game against Nevada in the first round of the NCAA Tournament. While playing for Creighton, he developed a unique ability to draw charging penalties while on defense.
After going undrafted out of Creighton in 2007, he spent the preseason with the Cleveland Cavaliers, making the opening-day roster, but never playing. He spent much of the 2007–08 season with the Iowa Energy of the NBA Development League, averaging 11.5 points and 6.4 rebounds per game,
He later joined collegiate teammate Nate Funk with Eisbären Bremerhaven of the German Basketball Bundesliga. Following a stint in Germany which saw him average 14.3 points and 7.3 rebounds per game, he was signed by the San Antonio Spurs in July 2008. Tolliver spent the early part of the 2008–09 campaign shuttling between San Antonio and Austin of the D-League. After appearing in 11 early games with San Antonio, he was sent to Austin for six games, where he averaged 17.8 points and 7.8 rebounds in his second D-League stint. He appeared in eight more games with San Antonio before being waived January 7, 2009. He signed with Iowa again shortly after; he then signed with New Orleans after three games with Iowa. After his ten-day contract expired without renewal, he returned to Iowa for a third stint. He was averaging 12.6 points and 8.1 rebounds per game with the Energy when he signed with Galatasaray Café Crown of the Turkish Basketball League. In December 2009, Tolliver was playing for the Idaho Stampede of the NBA Development League when the Portland Trail Blazers signed him to a short-term contract. The Blazers were able to temporarily sign a 16th player, one more than the usual league maximum, after the NBA granted the team a hardship exemption following a series of injuries to several key players. Tolliver played two games for Portland before being released on December 29, 2009, returning to Idaho.
On January 17, 2010, Tolliver was signed to a ten-day contract by the Golden State Warriors, who were also struggling with injuries. He was signed to a contract through the rest of the 2009–10 season on February 7, 2010. On April 7, 2010, Tolliver scored a career-high 34 points, shooting 14 for 22 from the field and 5 for 7 from the line. He also made one three-pointer and grabbed 8 rebounds. During the 2009–2010 season with the Warriors, he averaged 12.3 points and 7.3 rebounds per game.
On July 21, 2014, Tolliver signed a 2-year, $6 million contract with the Phoenix Suns. He went on to play 24 games for Phoenix in 2014–15 while averaging 3.3 points and 1.8 rebounds per game.
On July 9, 2016, Tolliver signed a 2-year, $16 million contract with the Sacramento Kings. On June 1, 2017, he was waived by the Kings.
Return to Detroit (2017–2018)
On July 14, 2017, Tolliver signed a one-year, $3.3 million contract with the Detroit Pistons. He finished second in 3-point shooting percentage in the league after shooting 46.1%, behind only teammate Reggie Bullock.
Return to Minnesota (2018–2019)
On July 9, 2018, Tolliver signed a one-year, $5.75 million contract with the Minnesota Timberwolves.
Return to Portland (2019–2020)
On July 3, 2019, Tolliver signed a one-year, $2.56 million deal with the Portland Trail Blazers.
Return to Sacramento (2020)
On January 20, 2020, Tolliver was traded back to the Sacramento Kings along with Kent Bazemore and two future second round picks in exchange for Trevor Ariza, Wenyen Gabriel and Caleb Swanigan. On February 29, 2020, Tolliver was waived by the Sacramento Kings after a contract buyout agreement was reached.
Memphis Grizzlies (2020–present)
On March 2, 2020, the Memphis Grizzlies announced that they had signed Tolliver to a 10-day contract. On June 22nd, the Grizzlies announced they would bring back Tolliver for the restart of the 2020 NBA season.
