Opener Kyle Coetzer led the charge with a superb 128 from 121 deliveries and combined in a 110-run stand for the fourth wicket with Richie Berrington (54 from 55).
Coetzer gradually ran out of partners, though. Scotland was dismissed for 294, which was a fine effort.
Otago spinner Nick Beard accounted for the tail, taking four for 54. But Tipene Friday was the pick of the bowlers with three for 30 from five overs.
The game was not a list A match, which meant both teams could change one player in their line-up. Otago seamer James McMillan bowled but did not bat, while Safyaan Sharif got through six overs for Scotland but was left out of the batting line-up.
Otago and Black Cap test opener Hamish Rutherford missed the game. He has returned to Dunedin due to a bruised hand. It is unclear how long he will be sidelined but the injury is not considered serious.
Michael Bracewell took Rutherford's spot at the top of the order and set the tone early, clipping four boundaries from an over on his way to a hard-hit 65 from 73.
Fellow opener Aaron Redmond batted in Bracewell's shadow early on but blossomed, whacking three sixes and seven fours in his knock of 71.
Sam Wells (38 from 47) and Iain Robertson (51 from 40) maintained the momentum and Derek de Boorder help steer the Volts past 300 with 69 from 37 deliveries. His innings featured 13 fours. Perhaps the only blemish was Otago lost its last four wickets for 11 runs.
Spinners Matt Machan and Michael Leask both picked up three wickets apiece.
Scotland's chase began in promising fashion until Friday arrived at the crease. The former junior Tall Black nicked out two wickets in his first over and then claimed a third a short time later.
The domestic twenty20 season will begin with an Island of Origin North v South clash.
The best available domestic cricketers will be representing their islands of birth.
The teams were chosen by the national selectors. The North Island will wear beige while the South Island will wear silver. Auckland's Kyle Mills will captain the North Island, with Peter Fulton (Canterbury) leading the South.
Entry to the game is free and it will be broadcast on SKY Sport and Radio Sport. North Island: Martin Guptill, Anton Devcich, Colin Munro, James Franklin, Colin De Grandhomme, Daniel Vettori, Derek De Boorder,Adam Milne, Kyle Mills (captain), Mitchell McClenaghan, Roneel Hira, Daryl Mitchell.
South Island: Michael Papps, Dean Brownlie, Neil Broom, Peter Fulton (captain), Brendon Diamanti, Andrew Ellis, Nathan McCullum, Ben Wheeler, Matt Henry, Jacob Duffy, Nick Beard, Logan van Beek.
