The Blues converted all four of their spot-kicks in the in the International Champions Cup match but the Spanish giants were left to rue Alen Halilovic's chip which came back off the bar and Thibaut Courtois saving from Gerard Pique.
It was an excellent end to the tour for Jose Mourinho's men, who went ahead through Eden Hazard's early strike only for Barca to turn the tide through second-half goals from Luis Suarez and Sandro Ramirez although Gary Cahill headed home four minutes from time to send the game straight to penalties.
Hazard gave the near 80,000 fans in attendance reason for cheer at the FedEx Field, Washington's NFL stadium, when he put Chelsea ahead after 10 minutes.
The Belgian collected the ball in Barca's half before shrugging off several challenges and poking past goalkeeper Marc-Andre ter Stegen.
Ivan Rakitic nearly drew Barca level almost immediately but saw a strike palmed over the bar by Courtois, while at the other end Oscar's strike came back off the woodwork.
Chelsea took their narrow lead into the interval but were pegged back six minutes into the resumption, Suarez scooping over Courtois, with Kurt Zouma clearing after the ball had already crossed the line.
A spate of substitutions appeared to suck the momentum from the game but Barca took the lead in the 62nd minute after Sandro cut inside and fired past Courtois.
However, Cahill bravely levelled in the 86th minute, leaping highest to head home from Willian's floated free-kick, with the England defender receiving a bloody nose from Barca substitute custodian Jordi Masip for his troubles.
That took the game to spot-kicks, where Radamel Falcao, Victor Moses, Ramires and Loic Remy were all on-target to give the Blues a confidence boosting win ahead of Sunday's Community Shield meeting with Arsenal at Wembley.
Source : PA
Source: PA