Puopolo made his debut for Norwood in 2007 and started out as a small forward/midfielder. Puopolo, who hails from Hope Valley, South Australia quickly built a reputation as the South Australian National Football League's best lockdown small defender. He was converted into a defender by former Norwood coach Trevor Hill in 2008. Despite his lack of height, he has always had the strength and speed to counter his rivals. In 2008 he was a SANFL Coca Cola Star Search Award Nominee. By the time he got drafted by Hawthorn at the end of 2010 he had played 68 senior games and kicked 13 goals for the Redlegs.
Puopolo made his debut for the Hawks in Round 7 of the 2011 AFL season against Port Adelaide. He is the AFL's ninth shortest player, standing at 173 cm. In his debut game, Puopolo had a reasonable performance, having nine kicks, six handballs and laying two tackles. He showed signs of being a tough-no-nonsense player. He has since flourished, playing initially in the Hawks' back pocket position and later as a defensive forward.
After making his debut in Round 7, Puopolo went on to play Hawthorn's remaining 19 games of the 2011 season, including three finals. His goal late in the Round 24 final quarter against Gold Coast sealed the match, along with his tackle soon after which thwarted a forward 50 entry - the win secured Hawthorn a top 4 ladder position for the finals ahead. Puopolo kicked 3 goals in the Semi-Final against Sydney, and 1 goal against Collingwood in the Preliminary Final. He finished his debut season with 20 games and 8 goals, gaining much experience in a brilliant first season. He was awarded Hawthorn's Best First Year Player Award.
He has carved a niche as a pressure forward who makes the most of his opportunities and enjoys a chase down tackle as much as a snapped goal.
In the 2012 AFL season Puopolo played in 21 out of 25 games and kicked 24 goals. He played in Hawthorn's loss to Sydney in the 2012 AFL Grand Final at the M.C.G., laying 7 effective tackles.
In the 2013 AFL season Puopolo played in 22 out of 25 games and kicked 15 goals. Puopolo became a Premiership player when Hawthorn defeated Fremantle in the 2013 AFL Grand Final at the M.C.G. in front of 100,007 people. In a typically ferocious performance he laid 6 effective tackles, and to seal the game halfway through the final quarter, his bouncing shot at goal was pounced upon by Bradley Hill who ran into an open goal to give Hawthorn a 5 goal lead which Fremantle could not overcome.