Rioli moved to Melbourne in 2004 as a 14-year-old, where he attended and boarded at Scotch College for four years whilst playing for the school's football team.
Rioli was also a standout performer in the 2007 AFL national under 18 championships, becoming the only Northern Territorian to earn All-Australian honours,[REF] following a seven-goal performance in a match against Queensland [REF].