A series of zirconium phosphate supported WOx solid acid catalysts with W loadings from 1–25 wt% have been prepared on high surface area zirconium phosphate by a surface grafting method. Catalysts were characterized by N2 adsorption, FTIR, Raman, UV-Vis, 31P MAS NMR, pyridine TPD and X-ray methods. Spectroscopic measurements suggest a Keggin-type structure forms on the surface of zirconium phosphate as a ([triple bond, length as m-dash]ZrOH2+)(ZrPW11O405−) species. All catalysts show high activity in palmitic acid esterification with methanol. These materials can be readily separated from the reaction system for re-use, and are resistant to leaching of the active heteropolyacid, suggesting potential industrial applications in biodiesel synthesis. © The Royal Society of Chemistry 2006.