Karen Hills' side remain undefeated on the road after a second-half Kayleigh Green penalty sealed the win for the Addicks.
The opening minutes saw both teams locked in an intense battle. In the 16th minute, Kayleigh Green had the opening strike of the game the forward leapt into the air, flicking her header goalwards. Her effort was met by the outstretched arms of Brook's, but the Blackburn Rovers' goalkeeper, denied Charlton the breakthrough.
Just two minutes later, Rovers retaliated as Shepherd sized up the distance between herself and the goal before unleashing a shot that sailed wide of the target, narrowly missing its mark.
Soon after Freya Godfrey weaved through a sea of Blackburn players, leaving a trail of defenders behind. She sped towards the box and attempted to curl the ball with finesse into the box. But the Rovers keeper' quickly reacted to gather the ball.
Green then looked to put the Addicks ahead unleashing a ferocious strike towards goal in the 30th minute as the Welsh international's shot hurtled through the air aiming to break the deadlock. But, Brook's came into action once again.
With time ticking towards the interval, Shepherd, the fleet-footed winger, dashed down the wing, collected the ball and aimed at the Addicks' net. But Rogers, standing tall between the posts, deflected the ball away with a fantastic save.
Shortly after the break, the Addicks took the lead after Green was brought down in the Addicks number 16 stepped up, and delivered with pinpoint precision as she calmly slotted the ball into the top left corner, a magnificent finish away from home!
In the 51st minute, Ayisi played a superb ball into the path of Green, who almost extended Charlton's lead, the forward attempted to poke the ball past the keeper, but Brooks showed great reflexes and made a fantastic save to deny her.
In the 73rd minute, Green found herself in a promising position once again. With a burst of speed, she created space for herself inside the final third and unleashed a powerful shot. But, her effort sailed over the goal, denying Charlton another opportunity to extend their lead. Charlton held firm and recorded an impressive three points to move up to fourth in the Barclays Women's Championship standings, three points off the top spot.
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Blackburn Rovers: Brooks, Toland, Williams (Dahou 79’), Shepherd (Smith 79’), Silcock, Huthings, Chandarana (Doyle 64’), Thomas (Hornby 64’), Walters (Ferguson 64’), Nokuthula
Subs (unused): Salgado (99) Coan (3) Robertson (22) Howarth (33)
Yellow card: Ferguson (68’)
Charlton: Rogers, McKenna, Ross, Ayisi (Johnson 78’), F. Godfrey (Humphrey 62’), Green, Skeels, Roche (Addison 62’), Bashford, O’ Rourke (Longhurst 46’), Roe
Subs (unused): Gray, McGowan, Muya, H. Godfrey
Yellow card: O’Rourke (28’)
Goal: Kayleigh Green (pen 48’)