McCullum made 68 off just 48 balls, including two sixes and seven fours, and shared a second-wicket stand of 114 with opener Hamish Rutherford (62) after Boyd Rankin struck early on his England debut to leave New Zealand one for one.
This was only the third time the Black Caps had made 200 or more in a Twenty20 international and just the fifth time in 59 matches in this format that England had conceded 200 or more.
England fielded just four survivors from the side that lost Sunday's Champions Trophy final to India, a 50 overs per side match reduced by rain to 20 for each team, in Eoin Morgan, Ravi Bopara, Jos Buttler and James Tredwell.
But with the exception of all-rounder Luke Wright (two for 31), the newcomers made little impression in the field.
After England stand-in captain Morgan won the toss, it took his fellow Irishman Boyd Rankin just four balls to take a wicket when James Franklin was out for a duck, wicket-keeper Buttler holding an inside edge.
But new ball partner Chris Woakes's only over went for 19, with left-hander Rutherford cashing in.
McCullum saw a top-edge off Rankin fly 83 yards for a six over Buttler's head and Rutherford was even luckier when, on 25, a mistimed cut off Jade Dernbach's first ball was dropped by Bopara at point.
Rutherford used his reprieve to slog-sweep and drive off-spinner Tredwell for two sixes in as many balls.
But, going for another big hit, off medium-pacer Wright, the seventh bowler used by England, he holed out to long-off having faced just 35 balls including four sixes and six fours.
Bopara, who produced a fine all-round performance against India on Sunday, then strayed down the leg side with a delivery costing five wides as McCullum continued to attack the bowling in an over costing 22 runs.
Wright however, struck again when he yorked McCullum before Ross Taylor's rapid 32 not out helped New Zealand past the 200 mark.