Virginia Tech blasted nine aces, and Virginia was beset by 10 service errors, allowing the Hokies to flip the script in a 25-21, 25-15, 18-25, 25-22 on Sunday.
Virginia out-hit Virginia Tech .173-.167 on the night, but the 19-point discrepancy in the service game was too much.
Sarah Billiard and Jayna Francis led Virginia (1-3, 0-3 ACC) with 12 kills each.
Alex Spencer set a career high with 27 digs in the loss.
Virginia Tech (4-1, 3-1 ACC) was paced by 17 kills from Kaity Smith and another 13 from Marisa Cerchio.