The England international pounced on 16 minutes to see the Villans claim the three points at Pirelli Stadium, with Willie Kirk's side falling to defeat in their first league fixture of 2024.
City's Manager made two changes from the side who beat Derby County 4-0 in the Adobe Women's FA Cup last weekend, with Yuka Momiki handed a full debut - having starred from the bench against the Ewe Rams - and Janina Leitzig back in between the sticks.
Momiki made her first Leicester start in the defeat.
That attack soon led to the Villa opener, however, with Leicester failing to clear a corner that Daly pounced on at the second attempt, volleying into the bottom corner just over a quarter of an hour in.
Carla Ward's side were now in the ascendency and could have doubled their advantage had it not been for a superb Leitzig stop to turn Alisha Lehmann's close-range effort behind after Adriana Leon sent a low cross into the box.
City's efforts to restore parity were almost realised when Momiki created space for a cross that was met by Shannon O'Brien but headed straight into Daphne Van Domselaar's arms.
That appeared to spark life back into the away side, as Leon charged down the right, going for goal herself from a tight angle and finding the stand behind the goal, though it wasn't far away from testing Leitzig. Anna Patten, unchallenged, headed wide soon after, keeping the score to one at the break.
Tierney led the side out in Burton.
Kirk responded for the second period, bringing on Deanne Rose and Josie Green, for Jutta Rantala and Sophie Howard, but it was one of the starting XI who opened up the Villa defence early in the half. Momiki worked space for a shot that forced Van Domselaar into a save before O'Brien hit the rebound over the top.
The contest continued to ebb and flow, with Leitzig required to palm away Leon's latest strike, before Courtney Nevin struck over the crossbar from Momiki's corner. The Australian full-back then looked to turn provider for captain Sam Tierney, whose header had to be dealt with by the Villa 'keeper.
Missy Goodwin's introduction, shortly followed by Aileen Whelan, added further attacking impetus to the Foxes' attack, though it was the away side who almost made their lead a more dominant one. City had Leitzig to thank again, getting a foot to Leon's shot in a one-on-one situation.
The German shot-stopper made several big saves but ultimately it wasn't enough for the Foxes.
A golden chance to level fell to Rose, who blazed the ball over at the back post. Leicester's best opportunity was still to come, though. The Canadian was this time kept out by Van Domselaar, only for substitute Ava Baker's first touch to be cleared off the line by Sarah Mayling in the aftermath.
A final flurry saw Whelan's shot blocked in the area and once Tierney couldn't beat the 'keeper in the box, time was up to find an equaliser. It leaves Leicester ninth in the WSL at the half-way stage, with a trip to Everton coming up a week on Sunday (2pm kick-off).
Before that, attention turns to the Continental Tyres League Cup on Wednesday night, with Leicester due back in Burton to face the Toffees in their final group stage match, aiming to progress into the knockout stages of the competition (7pm kick-off).
All times GMT.
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