Sam Tierney opened the scoring in the 20th minute but saw her side pegged back just before half-time through Charlie Wellings. But deep into added-time, Carrie Jones found a winner to guide the Foxes to three deserved points and a first success in five games.
There was one change to the City starting line-up that was beaten by Aston Villa last weekend, with Josie Green dropping to the bench to make way for Remy Siemsen in the XI, as captain Aileen Whelan was positioned further back in midfield.
In the opening 15 minutes, both sides looked to gain control of the match, with the first proper chance coming for the Foxes. A deep corner was met by the head Sophie Howard, who had made an intelligent run to the back post, but headed her effort over the bar.
The deadlock was broken by the home side when Courtney Nevin played a cross to the back post where the on-running Tierney was well placed to calmy guide a first time volley into the bottom right-hand corner.
City continued to threaten the Reading goal in search of a second, but failed to create a solid opening. The visitors did, drawing back level on the brink of half-time.
Losing possession in their own half, the Foxes felt hard done by, after making numerous blocks inside the box, before the ball found its way to Wellings, who rifled in from close range.
Up until the hour mark, there was little to report on as both sides searched for a second goal, however it was the hosts who looked most likely to score. Reading looked comfortable, though, knowing that a point would keep Leicester below them.
Leicester's next chance came through another Nevin-Tierney combination, when another deep cross was sent goalwards by City's No.3, but Grace Moloney was there to make the stop.
The pressure continued via two further chances in quick succession. First when Carrie Jones forced two saves from Moloney before Ashleigh Plumptre's header was kept out.
Minutes later, Leicester fashioned another opportunity. Siemsen, cutting in on her left, curled an effort onto the post before Whelan failed to convert the follow-up from close range.
The Foxes were throwing everything at Reading as Willie Kirk introduced Jess Sigsworth into the game. Immediately at the heart of the action, she played a ball into the box which Ruby Mace connected with but hit over the bar.
Leicester pushed and pushed in search of a late winner, and far out-weighed their opposition in terms of attempts on goal. Finally, deep into stoppage time, the Foxes pounced.
Inside the box, Hannah Cain supplied the ball to Carrie Jones, who, with a window of opportunity, fired low past Moloney to take the roof off King Power Stadium.
In what could be a season-defining moment, the Foxes will cherish three points, lifting themselves off the bottom of the WSL, a point clear of Brighton & Hove Albion.
Major moment - Carrie Jones' last-gasp winner
Carrie Jones ensured victory for the Foxes with a last minute strike inside the box.
With the game level pegging at the break, it was the Foxes who threatened in the second half, and had numerous chances to win it. Deep in stoppage time, the victory was confirmed when Carrie Jones, with half-a-yard of space, fired into the bottom left corner.
Who impressed - The Foxes
The team celebrate Carrie Jones' winner.
Sam Tierney and Carrie Jones scored the goals, but everyone in a Leicester City shirt played their part in a huge win on Filbert Way.
Where do we stand - 11th
The Foxes lift themselves out of bottom place in the WSL.
Three points places Leicester 11th in the WSL, one point ahead of Brighton & Hove Albion, and within touching distance of Reading ahead of them.
Coming up - Chelsea (A)
Leicester face Chelsea after the international break.
Next in the WSL, City will face Chelsea at Kingsmeadow on Saturday 23 April (2pm BST kick-off).
City: Leitzig; Bott, Howard, Plumptre, Nevin; Mace, Tierney, Whelan (C); C. Jones (Goodwin 90+13'), Siemsen (Sigsworth 82'), Cain (Green 90+10').
Subs not used: Levell, Purfield, Eaton-Collins, Pike, Robinson, Baker.
Goals: Tierney 20', C. Jones 90+6'.
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