His father Cyril Jr. was a champion footballer in the Northern Territory and the brother of the late Richmond Norm Smith Medallist Maurice Rioli.

His mother Kathy is the sister of Essendon two-time premiership player and 1993 Norm Smith Medallist Michael Long.

[3][4] Rioli moved to Melbourne in 2004 as a 14-year-old, where he attended and boarded at Scotch College for four years while playing for the school's football team.

He originally made the trip alongside his cousin Steven, after just three days in Melbourne the two re-packed their bags with the intention of returning home.

In an effort to retain the boys, Smith phoned Michael Long, who came out to the school with Derek Kickett and Sibby Rioli, another uncle.

[7] In this final year of junior football, he was one of five players, including Trent Cotchin, to be chronicled in the book The Draft: Inside the AFL's Search for Talent, by The Age journalist Emma Quayle.

[12] He covered 90% of his first pre-season schedule for the club; a very high volume of work for a first-year player according to the head fitness coach Andrew Russell.

[9] Rioli appeared in every game in his debut season, including an inspirational performance in Hawthorn's defeat of Geelong in the 2008 AFL Grand Final.

[16] Following his successful debut season and promising start to his second, he was compared to Gary Ablett Jr., who also began his career as a small forward with the potential to become a "dominant, match-winning midfielder".

Former footballer and journalist Garry Lyon said in an article for The Age, that when Rioli is ready to take on a greater workload in the midfield, will be determined by his physical and aerobic capacity.

Rioli's greatest challenge in the coming 12 months being to incorporate the "gut" running into his game that the likes of Ablett, Chris Judd, Lenny Hayes and Brett Kirk have mastered.

[3][19] His return was described as a "big boost" for Hawthorn's last-ditch bid to revive its season, after many commentators said the club was suffering a "premiership hangover".

"[3] After Hawthorn's demise in 2009, Rioli gave his support to a project which aims to teach Indigenous people in remote areas about the damage drugs and alcohol can do to the brain.

Sheree Cairney, the lead researcher at Menzies School, says there is a lack of knowledge in remote communities about how to treat drug and alcohol addiction, with the problem being "very, very widespread.

[28] Rioli married his childhood sweetheart, Shannyn Ah Sam, on 19 October 2014 at the George Brown Darwin Botanic Gardens.