All-rounder Nathan Smith led the way with a crisp innings of 96 from 120 deliveries to help his side post 324 for nine declared.
He stroked 11 boundaries and two sixes during his two and a-half hour stint at the crease.
The 20-year-old's innings helped Otago overhaul Canterbury's total of 287 for nine.
Josh Finnie also shone with 71 from 66, while Mark Craig's knock of 52 from 95 provided some backbone in the lower order.
At stumps, Canterbury was four without loss trailing by 33 runs with a day to play.
Earlier, runs were hard to come by as opener Brad Wilson struggled to get the scoreboard moving.
The Volts resumed on five for two with Wilson unbeaten on two. He added another four runs to his overnight total but helped take some energy out of the attack on a slow wicket.
Carisbrook-Dunedin captain Cam Hawkins also showed some grit with 37 from 111 balls.
Their resolve helped the rest of the order flourish.
Finnie was the first to capitalise with a fluent innings which included five sixes and six fours.
His innings help swing the innings from defence to attack.
Andrew Hazeldine was the pick of the Canterbury bowlers with two for 21 from 12 overs, while Will Williams' two for 48 from 20 overs was an honest return as well.
Otago top-order batsman Shawn Hicks did not take his place in the batting line-up.
He has a thigh injury and is being rested.
Meanwhile, Volts fast bowler Michael Rae has returned from a stint in Sydney with a shoulder niggle and is unlikely to be fit for Otago's opening Plunket Shield match against Northern Districts next week.
