In the study, a novel electrochemically modified carbon nanofibrous anodic membrane (G/SnO2/CFs) is observed to be effective toward electrochemical oxidation of main emerging and refractory pharmaceutical. By innovatively incorporating graphene/tin dioxide (G/SnO2) into carbon nanofibers (CFs), the electrooxidative performance and conductivity can be improved significantly by the significant electrooxidation capacity of SnO2 and excellent electrical conductivity of graphene. Herein, the electrochemical filtration and degradation efficacy of the PAN-based G/SnO2/CFs microfiltration (MF) membrane filter was evaluated by the electrochemical degradation performance of refractory toxic organic - sulfamethoxazole (SMX). The study proved that, the increased anodic membrane amount and flow-through mode lead to enhanced degradation performance. 9 non-toxic smaller intermediates of SMX were identified by LC-MS/MS, so that the SMX transformation pathway was proposed. The excellent SMX degradation performance (85% removal efficiency) and membrane stability (10 cycles up to 50 h reaction) suggests the potential of G/SnO2/CFs MF membrane filter to treat the refractory toxic organic from wastewater.