An efficient and selective solvent free protocol is illustrated for the acetylation of alcohols via the exposure of neat reactants under microwave (MW) irradiation, in conjunction with the Mediation of acidic H5PM10V2O40 (M = W, Mo) and some other mixed addenda Keggin-type heteropolyoxometallates as catalysts in really, short reaction times (<5 min). The two above, modified catalysts showed good catalytic activity in the acetylation protocol and revealed more reactivity than the Si substituted H7SiW9V3O40, H4SiW9Mo3O40, and HsSiW9Mo2VO40 catalysts In this methodology, water is the only byproduct and, notably, the aspect of effluent treatments does not arise. The salient features of this high yield protocol were enhancement of the reaction rate and the experimental ease of manipulation.