The electric field assisted membrane bioreactor (MBR) is an effective technique to alleviate membrane fouling. In this study, the spontaneous electric field was introduced into the MBR to observe the growth process of cake layer on the membrane surface. The external resistance for spontaneous electric field MBR (S-50) and S-500 were 50 Ω and 500 Ω respectively. During the experiments, S-50 maintained the highest electric field intensity of 11.83 mV/cm. The reduction of extracellular polymeric substances (EPS) content in activated sludge, transmembrane pressure (TMP) growth rate reached 52.8% and 51.7% respectively. After 28 days operation, S-50 obtained the minimum contaminant specific biovolume (23.316 μm3/μm2), which was 68.2% lower than that of it in Control-MBR. The metal oxide or metal hydroxide were distributed in the cake layer. EPS played a significant role in the formation and growth of the cake layer. Based on the results obtained in this study, the growth of the biofouling layer on the membrane surface could be divided into three stages. EPS first deposited on the membrane surface, and then microorganisms embedded in the cake layer to form clusters. After that, EPS and total cells further increased and led to a faster biovolume growth rate. Subsequently, the biovolume growth rate decreased in the cake layer. The spontaneous electric field delayed the deposition of EPS on the membrane surface. The produced H2O2 and •OH were beneficial to the degradation of organics, causing the smaller contaminant biovolume on the membrane surface. This work aims to provide a theoretical basis for the practical application of the electric field to control membrane fouling.