All five goals were scored by former Portadown players as Ballymena got their season off to a promising start.
New signing Alan Teggart pounced on a mistake to shoot a 10th-minute opener but Gary Liggett fired in an equaliser.
Gary McCutcheon restored the lead for the Sky Blues, scoring from close in after James Costello's cross.
Costello missed a penalty in the second half but Jordan Baker and McCutcheon were on target before Ballymena had Tony Kane sent-off late on.
So, a fine start to the Irish Premiership season for Roy Walker's new-look United side.
They got that dream start when Teggart slotted his shot past Whites keeper Billy Brennan and could have been two up as Baker hit the bar with an acrobatic volley.
Distillery got their equaliser in the 34th minute when Aaron Callaghan's deep cross was met by David Cushley and, when his header was pushed out by keeper Aaron Kerr, Liggett smashed in from close range.
Ballymena regained the lead through McCutcheon in the 38th minute and then fluffed a penalty early in the second half as Costello shot high and wide after Aaron Traynor's hand ball.
Baker squeezed a header in from a Costello cross in the 64th minute and then McCutcheon got his second to complete an emphatic United victory.
The only blot for the visitors was Kane's late red card.