"David Keith Brennan, 49, from Neath, was arrested after police were called to the Ambassador Hotel in central Barcelona just after 0200 GMT Friday.
Mr Brennan's brother-in-law, Stephen Storey, 47, also of Neath but born in Liverpool, had died.
The Foreign Office said Mr Storey's next of kin had been informed.
The incident happened at the hotel off the Ramblas in the city's Ciutat Vella district.
A spokesperson said: 'We can confirm the death of a British national in Barcelona.
'We have notified next of kin and are providing consular assistance.
'We can confirm the arrest of a British national in Barcelona on 4 February. We are providing consular assistance."
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