A special unit was waiting for the man inside the shop Passeig de Gracia, Barcelona's biggest shopping street.
Interpol believes the gang carried out at least 380 armed robberies jewellery shops between 1999 and 2015.
Most of those arrested are from eastern Europe.
One of the men robbing the shop was armed, police said. German and Serbian authorities were involved in the build-up to the raid.
In February 2014, Pink Panther gang member Borko Ilincic was arrested in Madrid. He was accused of being involved in the spectacular robbery of a jewellery store in Dubai's al-Wafi Mall in 2007.
He appeared in court in Dubai for the first time in June after his extradition to the United Arab Emirates.
Many of the gang's members hail from the Balkans and have also hit Tokyo and London. Interpol estimates they have stolen close to â‚¬334m ($371m; Â£283m) of jewellery.
The Pink Panthers were given their name when police in London made an arrest in 2003, and found a diamond ring hidden in a jar of face cream - a ploy used in the original Pink Panther comedies starring Peter Sellers.

The charity said tests confirmed all of the cats near Victor Avenue, in Melton Mowbray, Leicestershire, had ingested the toxic substance.
In the most recent case, seven-month-old Meereen died on Monday.
An RSPCA spokesman said it was unclear whether the poisonings were accidental or deliberate.
Updates on this story and more from Leicestershire
Three other cats in the area have died in the last seven days, while another cat died two weeks ago.
Meereen's "devastated" owner, Adria Pearce, said the cat came home on Friday evening and "seemed to be shivering a little".
"I haven't been able to stop crying since she died," she said.
"We found her behind the sofa, where she was foaming from the mouth and trying to be sick."
Meereen was taken to the vets - where it was confirmed she had consumed antifreeze - and died three days later.
RSPCA inspector, Andy Bostock, is appealing for everyone in the area to ensure pesticides and chemicals were stored safely.
"We are very concerned," he said.
"It is the time of year where people use antifreeze in their cars, so if you do, please make sure there are no leaks and any spills are cleaned up properly."
Police in Barcelona have arrested five suspected members of the so-called "Pink Panthers" gang as they tried to rob a jewellery shop.
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Five cats have died from antifreeze poisoning on or near the same street in the space of two weeks, the RSPCA has said.