Tommy Rowe missed the crucial penalty for Doncaster as Charlton set up a repeat of one of the greatest ever play-off finals against Sunderland.
Doncaster captain Rowe had the chance to take the shootout to sudden death after teammate John Marquis and Charlton's Naby Sarr saw their spot-kicks saved.
But he blazed wide to spark wild scenes of celebration at the Valley as Charlton progressed to the League One play-off final and secured a return to Wembley for the first time since they faced Sunderland there in 1998.
Doncaster had a mountain to climb after they went behind inside two minutes to fall 3-1 behind on aggregate.
But they fought back through goals in normal time from Rowe and Andrew Butler to force extra time.
Marquis then edged Grant McCann's side further ahead only for Darren Pratley to respond immediately for Charlton and make it 4-4 on aggregate and send the game to a shootout.
Charlton are no strangers to a 4-4 play-off draw. Their final against Sunderland 21 years ago finished that way after extra-time before the south Londoners triumphed 7-6 on penalties to reach the Premier League.
And following the repeat of that goal crazy score line by the end of this roller-coaster, nerve-shredding 120 minutes there was more spot kick joy to come for the south Londoners after Rowe sent his decisive kick into the stands.
Charlton, who have suffered so much during the club's demise under Roland Duchatelet, had not had a night as big as this one to enjoy for some time.
The Valley was rocking and sold out for the first time since 2012, with over 25,428 fans squeezed in.
And those here for the home team lifted the roof off the stadium after just one minute and 48 seconds when Bielik head in Josh Cullen's free-kick.
Things might have quickly got even better as Albie Morgan and Anfernee Dijksteel gave Doncaster further scares. Doncaster, to their credit, stayed calm under the pressure from Charlton and the raucous atmosphere.
And Rowe punctured it when he burst into space and smashed in a stunning strike from 25 yards. Charlton needed Dillon Phillips' sharp save to deny John Marquis a second for the visitors soon after their 11th minute equaliser.
Rowe miscued a presentable headed chance early in the second half that would have drawn Doncaster level and the natives, who provided the energy in the first-half, were nervous as Charlton struggled to rediscover their early intensity and effectiveness.
Talismanic striker Lyle Taylor created a rare clear chance for either side but Josh Parker couldn't quite direct his cross on goal.
And how costly that turned out to be. Firstly defender Andrew Butler struck with two minutes of normal time left to force an extra 30 minutes.
Ten minutes into the added period former Millwall striker Marquis then thought he had won it with a header from Mallik Wilks's cross only for Charlton to go up the other end and see Pratley poke in after Marko Marosi failed to hold Taylor's cross, paving the way another unforgettable play-off penalty shootout win for the Addicks.