A novel method of cellulose degradation is investigated in this paper. In this work, a three-electrode system, which contains a Pb/PbO2 anode, two copper cathodes and a reference saturated calomel electrode (SCE), is applied to electrocatalytic degradation of cellulose. The composition of the products in filtrate is characterized by phenol-sulfuric acid method, NMR and GC-MS. In addition, the solid sample is analyzed via Ubbelohde capillary viscometer and FT-IR spectra. The results suggest that it is effective to convert cellulose to soluble sugar, 5-hydroxymethylfurfural (5-HMF) and other products by electrocatalytic method. The reaction mechanism of cellulose degradation is also discussed.