As a 21-year-old in 1995, Urbina made seven pitching appearances, starting four, and went 2–2 with a 6.17 ERA. In 1996 he established himself on Montreal’s pitching staff, as he hurled 33 games, including 17 starts and a career-high 114 innings, and posted a 10–5 record with a 3.71 ERA. His career as a closer began In 1997, when he collected 27 saves with a 3.71 ERA and a 5-8 record in 63 relief appearances.

Urbina started his career as a middle reliever with the Montreal Expos, where he pitched for six seasons and was an All-Star once, in 1998.

Urbina improved in 1998, going 6-3 with 34 saves and a 1.30 ERA in 64 games. In 1999 he topped the National League with 41 saves, while notching a 6-6 record and a 3.69 ERA in 71 contests.

On April 4, 2000, Urbina struck out three batters on nine pitches to tie a Major League record. Nevertheless, he was limited to 13 appearances and ended the year with a 0-1 mark, eight saves and a huge 4.05 ERA.

Urbina earned his second All-Star berth in 2002, when he went 1-6 with 40 saves and a 3.00 ERA in 61 games.

Urbina signed as a free agent with the Texas Rangers on December 23, 2002. He went 0-4 with 26 saves and a 4.19 ERA in 39 games for the Rangers in 2003 before being traded during the midseason.

On July 11, 2003, Urbina was traded by Texas to the Florida Marlins in exchange for Adrián González, Ryan Snare, and a minor leaguer. For the remainder of the season, Urbina served as a setup man for Marlins closer Braden Looper, going 3-0 with six saves and a 1.41 ERA in 33 games. He posted a combined record of 3-4 with 32 saves and a 2.81 ERA in 54 appearances during the 2003 season.

Urbina signed a two-year contract with the Detroit Tigers on March 29, 2004. That marked his last year where he was closer for at least part of the season. In 54 games, he went 4-6 with 21 saves and a 4.50 ERA. He began the 2005 season in good form, collecting a 1-3 record with a 2.63 ERA while contributing with nine saves, but then found himself on the move again for the third time in his career.

In September 2004, Urbina’s 54-year-old mother, Maura Villarreal, was kidnapped and held for a $6 million ransom in southwest Venezuela. Urbina’s family refused to pay the ransom and an anti-kidnapping unit rescued her in a military-style operation on February 18, 2005.

On June 8, 2005, the Tigers traded Urbina along with infielder Ramón Martínez to the Philadelphia Phillies in exchange for second baseman Plácido Polanco.

He made his last Major League appearance on October 2, 2005, during a 9–3 Phillies victory over the Washington Nationals at RFK Stadium.

On November 7, 2005, Urbina was arrested in Venezuela on a charge of attempted murder for an incident that occurred on October 16. Urbina attacked five farm workers on his property whom he had accused of stealing a gun, wielding a machete and attempting to pour gasoline on them. On March 28, 2007, Urbina was convicted of attempted murder and sentenced to fourteen years and seven months in prison. He was released on December 24, 2012, after serving just over seven years of his sentence.