Arsenal underlined their dominance of the women's game by lifting the FA Cup to complete a historic Quadruple.
Ludlow (right) celebrates putting Arsenal ahead
The Gunners were rocked inside two minutes when Eni Aluko crossed for Katie Holtham to put Charlton ahead.
But Arsenal levelled through Kelly Smith's free-kick and were ahead after 15 minutes when Jayne Ludlow scrambled home Lianne Sanderson's free-kick.
Ludlow's spectacular volley made it 3-1 just before half-time before Smith wrapped up victory late on.
Charlton were the last team to beat Arsenal - in the 2006 League Cup final last April - but since then, the Gunners have won a fourth straight Premier League title, the League Cup and their first Uefa Cup.
Monday's game was played in front of 24,529 fans at Nottingham Forest's City Ground - almost double the previous crowd record for the Women's FA Cup final of 13,824 in 2001.
The pre-match odds suggested they might be in a for mismatch, the Addicks beginning the match as 20/1 outsiders.
But Keith Boanas' side made a dream start, as England striker Aluko skipped into the box and delivered the perfect ball for Holtham to bundle home.
But Arsenal, who recovered from 2-0 down to beat Charlton 9-2 in the league in April, were only briefly rattled.
Maria Bertelli's hopelessly late challenge on Smith earned the Charlton defender a deserved booking - but worse was to follow.
Keeper Toni-Anne Wayne reacted slowly to Smith's subsequent free-kick, perhaps believing it would drift wide, but the ball hit the back of the net and the Gunners were level.
Eight minutes later, they went ahead when skipper Ludlow took advantage of some poor defending to tap in - albeit with a deflection off Jessica Smith.
But Charlton dug in, and with the effervescent Aluko a constant threat up front, they looked to be heading for half-time with hope.
Ludlow's second goal, then, was a cruel blow for the underdogs - and once again keeper Wayne was left red-faced.
The Wales international's volley was sweetly struck but the Charlton keeper was again slow to get across her goal as Arsenal stretched their lead moments before half-time.
The Gunners had plenty of chances to further that lead in the second half, Sanderson and Julie Fleeting shooting straight at Wayne, Rachel Yankey hitting the post and substitute Gemma Davison angling a shot narrowly wide.
Charlton's best chance of the second half came when Aluko broke away and shot through Emma Byrne's legs - but the ball deflected off the Arsenal keeper and safely behind.
The Gunners finally scored a fourth when Smith turned beautifully in the box and though Wayne got a hand to the England striker's shot, the ball bobbled in.
Arsenal Ladies: Byrne, Ludlow, Grant, Smith, Sanderson (Carney 63), Fleeting (Davison 76), Yankey, Scott, Chapman, Asante, Phillip.
Subs Not Used: White, Larkin, Spencer.
Goals: Smith 7, Ludlow 15, 45, Smith 80.
Charlton Women: Wayne, Casey Stoney, Holtham (Hughes 83), Hills, Bertelli, Murphy, Aluko, Dowie (Heatherson 83), Potter, Smith (Hincks 70), Boyer.
Subs Not Used: Cope, Hicknock.
Goals: Holtham 2.
Ref: A Bates (England).