Rioli publicly admitted to having smoked marijuana with other club members the night before his drug test, and attempted to swap his tainted urine with a clean sample in a Gatorade bottle.

[5] He was subsequently issued with an indefinite suspension from the AFL, and ruled out from competing with the West Coast Eagles in that year's Finals series.

[7][8] On 23 April 2021, Rioli was transiting through Darwin Airport where he was stopped and searched after drug detection dogs gave a positive indication that he was carrying an illicit substance.

Rioli was scheduled to play his first game back in round 23 of the 2021 AFL season but was ruled out the week prior due to a tight hamstring.

[11][12][13] Rioli requested a trade to Port Adelaide at the conclusion of the 2022 AFL season in a move that Eagles CEO Trevor Nisbett described as "bitterly disappointing".