Those expecting to see Williams continue to battle back after a difficult child birth last year were left disappointed as the 36-year-old committed 25 unforced errors to Konta's nine and managed to put just 41 percent of her first serves into play.
"I think she played well in the second set and I think I wasn't sharp at all in the first set and she got confident and she clearly ran away with it," the American said after the loss.
Williams, who lost the Wimbledon final earlier this month to German Angelique Kerber, had never lost a match before where she did not win at least two games since turning pro in 1995.
As poorly as Williams played, the 27-year-old Konta was sharp, firing six aces and smacking 17 winners to Williams' nine while controlling the tempo of the match.
"She obviously wasn't playing at her best level, nowhere near it, and I really just tried to play the match on my terms," said Konta, who won the tournament two years ago.
"I tried to put aside the incredible champion she is and just play the player of the day," she said.
"I felt I did better than her on the day but it's still a humbling experience to be out here with her."
With the loss Williams falls to 11-4 since returning to the tour and will look to bounce back when she competes in the Cincinnati Open next month, another hard court tune-up ahead of this year's U.S. Open.
Konta will face American teenager Sofia Kenin in the second round.
(Reporting by Rory Carroll; Editing by Amlan Chakraborty)
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