At the 1991 NFL Draft the Raiders selected Marinovich in the first round; he was the 24th pick overall and the second quarterback taken—ahead of Brett Favre—signing a three-year, $2.25 million deal. Marinovich made his NFL debut on Monday Night Football, in an exhibition game against the Dallas Cowboys on August 12, 1991. Entering the game with 15 minutes remaining, he moved the Raiders downfield, completing three of four passes for 16 yards and a touchdown. He did not start a game until Jay Schroeder was injured before the final week of the season, where he impressed observers with 23 completions in 40 passes for 243 yards against the Kansas City Chiefs in a close loss. Because of this great debut he started the following week against the Chiefs in the playoffs, but was very poor, throwing for just 140 yards with 4 interceptions in a 10-6 loss and smashing a locker room mirror with his helmet after the game.
After the Raiders began 0-2 in 1992 with Schroeder as quarterback, Marinovich became the starter. He threw for 395 yards in a loss in his first start that season and lost the following week as the Raiders started 0-4. He then won three of his next four games before losing to the Dallas Cowboys. Marinovich's best game during that span was against the Buffalo Bills on October 11, 1992, in which he completed 11 of 21 passes for 188 yards and two touchdowns in a 20-3 victory. The following week Marinovich started against the Philadelphia Eagles, seeing three of his first 10 passes intercepted. Schroeder regained the starting job and Marinovich never played again in the NFL.
Marinovich had serious substance abuse issues throughout his NFL career. During his rookie season, he increased his partying and drug use beyond marijuana, including taking pharmaceutical amphetamines before games. Because of his college arrest for cocaine possession, the NFL required him to submit to frequent drug tests. Marinovich passed the tests using friends' urine, but after using the urine of a teammate who had been drinking heavily, the test registered a blood alcohol content four times the legal limit and caused the Raiders to force him into rehabilitation. The Raiders held an intervention for him after the season, and Marinovich spent 45 days at a rehab facility. In the 1992 season Marinovich shifted to using LSD after games, because it would not show up on the drug test. His play suffered and his coaches complained he was not grasping the complex offense. He failed his second NFL drug test and went back into rehabilitation. In training camp before the 1993 season, Marinovich failed his third NFL drug test, this time for marijuana, and was suspended for the 1993 season. The Raiders released Marinovich on the final cutdown, choosing not to pay for Marinovich's salary while being suspended in the year before the salary cap would go into effect.
In 1994, once Marinovich's suspension was lifted, the Pittsburgh Steelers showed some interest in signing him to be their third-string quarterback behind Neil O'Donnell and Mike Tomczak. Marinovich, not liking the culture of the NFL, chose not to return to the league. The Steelers ended up turning to the NFL Draft instead, drafting Jim Miller.
ESPN released a documentary film about Marinovich titled The Marinovich Project, which was shown after the Heisman presentation for 2011.
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