Having won the 2000 NRL Premiership, the Broncos traveled to England to play against 2000's Super League V Champions, St Helens R.F.C. for the 2001 World Club Challenge, with De Vere playing at centre and kicking three goals in Brisbane's loss. Later that season he joined the ranks of Brisbane players (Terry Matterson, Glenn Lazarus, Luke Priddis and Chris Johns) to have represented New South Wales against his Broncos teammates in a State of Origin match. He also set the Broncos record for most goals in a match when he kicked 9/9 in a 50–6 win over the North Queensland Cowboys in 2001. He was again top point-scorer for the Broncos in 2001, 2002 and 2003.