The bandy legged 23-year-old German was snapped up during the summer on a free from Turkish football and was immediately christened Carlos by the Oakwell fans.
The Samba-style was evident 30 seconds before half-time when Werling lined up for a 30-yard free-kick and smashed it in as keeper Roman Larrieu and his defence watched in jaw-dropping admiration.
But Plymouth, who arrived boasting an unbeaten start to the season and an impressive end to last term, came within a whisker of a point with two goals in five minutes and an amazing second-half fightback.
The south coast outfit looked lively in the opening ten minutes, but it was Barnsley who grabbed the initiative in the 12th minute with Hungarian Istvan Ferenczi's second goal of the season.
Lewin Nyatanga picked out lanky frontman Kayode Odejayi , whose stretched his legs and powered into the area before cutting a neat pass across for his strike partner to slot home a cool shot.
Plymouth came close to levelling after 36 minutes when a low cross from Peter Halmosi skidded across the face of goal and David Norris was a fraction away from a scoring connection.
And in the dying seconds of the half after Barnsley's second, Akos Buzsaky tried his own long range free-kick which he threaded powerfully between a crowd of defenders but keeper Heinz Muller save superbly.
Four minutes into the second half another super save came from Muller, who reacted smartly to turn over a close-range header from Marcel Seip after a pinpoint corner from Buzsaky.
Plymouth continued to make the running and Norris went within a fraction of a reply after 53 minutes, but his glancing header was inches wide.
Brian Howard headed in Anderson Silva's super cross for the third after 60 minutes and prompted Plymouth boss Ian Holloway into a triple substitution two minutes later and his side immediately pulled one back with a Barry Hayles header and added a second five minutes later from substitute Nick Chadwick in a thrilling finish.