The appointment follows on from the resignation of former principal Christina Herrick on medical grounds last October.
Deputy principal Paul Bolton has been acting principal since then and said he had been privileged to do so.
Mr Hunter addressed the full school assembly of just under 1000 pupils and said he was pleased to take up the new role.
The 44-year-old had been a pupil of the college in the 1980s and was named best all-round sportsman in both 1985 and 1986.
Mr Hunter had his last day at Maniototo Area School on Friday having been being its principal for three years.
His new school had about 800 more pupils than Maniototo, which he said would be a challenge when getting to know everyone.
''I also look forward to getting to know the pupils here.''
Mr Hunter said all pupils were welcome to share opinions with him and his door would always be open.
''Never make excuses. I'm not into that ... The only thing you have control over is your attitude and, ultimately, that is what will lead to success.''
Before his time at Maniototo, Mr Hunter was deputy principal at Roxburgh Area School, and taught at St Kevin's College (Oamaru) and Tauranga Boys' College.
He hoped to compete with all Dunedin schools, academically and on the sports field, he said.
Mr Hunter is expected to have a sporting influence on the school after coaching Maniototo premiers in the Central Otago Rugby competition this year and several first XV sides including at St Kevin's College.
He has been an Otago cricket representative and played rugby for Otago and South Canterbury.
