It comes just days after the cafe chain had revealed on Wednesday it has been notified of “significant and potentially fraudulent” accounting irregularities.
Mr Marsh was suspended from his role while the circumstances of the financial black hole were investigated.
Patisserie Valerie, which has 206 cafes in Britain and 2,500 staff, revealed this week it was teetering on the brink of survival and was in need of an “immediate cash injection” to continue trading.
The firm could be forced to appoint administrators as early as Friday.
To add to the company’s woes, Patisserie Holdings has also just become aware of a winding-up petition against its principal trading unit Stonebeach.
It related to more than £1.14 million said to be owed to HMRC.
The chain’s owner Patisserie Holdings said: “The company has been made aware that Chris Marsh, who is currently suspended from his role as company finance director, was arrested by the police last night and has been released on bail.
“Further updates will be released in due course as appropriate.”
Hertfordshire Police said: “A 44-year old man from St Albans has been arrested on suspicion of fraud by false representation.
“He has been released under investigation.”
Chairman Luke Johnson is said to be considering stepping in with funds that could help save the business.
Mr Johnson, a serial entrepreneur, is the largest shareholder in Patisserie Holdings with a 37 percent stake.
Shares were trading at 429p before being suspended, valuing the business at £440 million.
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