Paul Whelan, 48, was held on December 28 over claims a memory stick containing a list of spooks was found in his hotel room.
The former US Marine lives in Michigan but was born in Canada to parents from the West Midlands. He holds British and US citizenship.
His librarian brother David said he was in Moscow to help plan the wedding of another ex-Marine.
He told The Times: “We are deeply concerned for his safety and well-being. His innocence is undoubted and we trust his rights will be respected.”
He said his bachelor brother, who now works in corporate security for a US car parts firm, had been to Moscow several times to meet pals from a Russian social media site.
Daniel Hoffman, a former CIA Moscow station chief, said it was “possible, even likely” President Vladimir Putin had ordered Whelan’s arrest in a swap bid for a female Russian agent who infiltrated the National Rifle Association.
A Russian news agency yesterday claimed Mr Whelan denied the charge.
The Foreign Office said: “Staff requested consular access to a British man detained in Russia after receiving a request for assistance.”
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