Polyoxymethylene dimethyl ethers (PODEn) are extremely effective diesel additives to reduce soot formation during combustion. We introduce a series of Fe-Zn composite solid acid catalysts (SO42-/xFe(2)O(3)-yZnO), for the condensation reaction of methanol and paraformaldehyde (PF) with a cheap and feasible route to efficiently synthesize PODEn. These catalysts were characterized by different characterization techniques, namely BET, XRD, SEM, EDS, FTIR, and NH3-TPD and the results showed that Fe/Zn molar ratios strongly influenced the physicochemical characteristics of catalysts, thus affecting the methanol conversion and PODE1-6 and PODE3-6 selectivity. Accordingly, the methanol conversion was decreased and the selectivity of PODE3-6 was increased after increasing the Zn molar content. Comparatively, SO42-/Fe2O3-2ZnO exhibited superior catalytic activity among the various investigated catalysts due to the high acid density of strong acid sites. The optimal reaction conditions were observed to be at a 3.0 wt% catalyst loading (catalyst/reactant mass ratio), 2.5 hours ours of reaction time, a reaction temperature of 403 K, and a molar ratio of 3:1 of CH2O to methanol, achieving a high selectivity of 99.09% PODE1-6 and 28.23% PODE3-6 with 55.16% methanol conversion during the reaction.