As part of our continued effort to achieve the synthesis of halohydrin esters from polyols by a sustainable method, here we report on a multicomponent inorganic acid-mediated solvent-free synthesis. The synthesis was designed to ensure few waste materials. Using this approach, the process shows a low E-factor and a high reaction mass efficiency. The new process involves the preparation of a reaction mixture containing either a fatty acid or fatty material, glycerol or diol, a halide salt and H3PO4. This mixture is heated at 100 °C for 48 h, yielding up to 88% of halohydrin ester. The process also allows recovery of pyrophosphate salts, compounds that have various applications in agriculture, and in the pharmaceutical, chemical and food industries. ; This work was supported in part by a Grant-in-Aid from the Secretarı´a de Estado de Polı´tica Cientı´fica y Tecnolo´gica of the Spanish Ministry of Education and Culture (Contract grant number: CTQ2009-14699-C02-01).