The aim of this investigation was to develop an efficient, rapid, and selective method for the synthesis ofω-alkylenediphosphoric acids (HO)2(O)P-O-CH2n-O-P(O)(OH)2from reaction of several diols with phosphorus oxychloride. The reaction was investigated using three methodologies: (i) presence of a base, (ii) classical heating, and (iii) use of microwave irradiation. Influence of reaction temperature and molar ratio of reagents, as well as the nature of the solvent, was studied using these three different methods.