According to Spanish sports daily Marca, Valencia president Vicente Soriano refused the bid without hesitation.
This was as part of a promise that he'd made to the fans upon his assuming the office of president last month that neither Villa nor David Silva, two of the club's crown jewels, would be moved on for a quick profit.
Marca claims that Soriano made the final 'no' decision this afternoon at a board meeting in which at least a couple of directors were in favour of accepting the lucrative offer.
Also present was first team coach Unai Emery, who appeared to have been invited in order to be kept informed of developments regarding his top forward.
Madrid, meanwhile, may plot another bid as they look to pre-empt Robinho's possible departure to Chelsea.