The decomposition of polyoxymethylene dimethyl ethers (PODEn) with and without the presence of water was investigated. Without water, the products from the decomposition of PODEn (n = 25) contained smaller (PODEn(-i)) and larger (PODEn (+ i)) homologues that followed the Schulz-Flory rule. However, the products from the decomposition of PODEn (n = 15) in water contained only formaldehyde (FA), methanol and dimethoxymethane without any other PODEn (+/- i). The reaction kinetics showed that the decomposition of PODEn in water was pseudo-zeroth order with respect to PODEn. The rate constants with pre-exponential factors and apparent activation energies were obtained for the decomposition reactions in water. Based on the above results, PODEn (n = 15) were used as reactants to react with phenol for the synthesis of bisphenol F (BPF) catalyzed by phosphoric acid. PODE2 was found to be better than FA for the synthesis of BPF with the improved yield and selectivity.