The BF(3).OEt(2)-promoted nucleophilic substitution of alpha-aryl-alpha-ketophosphates to afford alpha,alpha-diaryl ketone products is described. Electron-rich alpha-ketophosphates perform best, with electron-neutral and electron-poor substrates also tolerated. The reaction is tolerant of a range of aromatic, heteroaromatic, and nonaromatic nucleophiles, with yields ranging from 44% to 84%. Enantioenriched starting material yields racemic product, suggesting an S(N)1 pathway via an acylcarbenium ion.