Composite matrix of epoxy copolymers P (GMA-co-MPC)) and acetylene black (AB) was firstly used to entrap cytochrome P450 (CYP3A4). The direct electrochemistry behaviors of CYP3A4 were investigated and CYP3A4 immobilized in P(GMA-co-MPC)/AB film exhibited excellent electrocatalytical activity to diethylstilbestrol (DES). CVs of CYP3A4/P(GMA-co-MPC)/AB/GCE. (a) N2-saturated+2μM DES, (b) air-saturated, (c) air-saturated +2?μM DES