Abstract: A novel ionic liquid, 3-{[{4-[((carbamoyl)amino)ethylmethacrylate]butyl} ((carbamoyl)amino)ethylmethacrylate]propyl}-1-ethenyl-1H-imidazol-3-ium bromide (CCPEimBr) functionalized with vinyl, amino and methacrylate groups, was synthesized and characterized with 1H-NMR, FTIR and HPLC-MS. CCPEimBr was adopted as the functional monomer to prepare a molecularly imprinted polymerized ionic liquid hydrogel film on a glassy carbon electrode surface for human epididymis protein 4 (HE4) sensing. Gold nanoparticles (AuNPs) and ZnCdHgSe QDs were incorporated into the imprinted film as photoelectric active materials. The photocurrent response was measured to investigate the sensing performance of the imprinted sensors towards HE4. The imprinted photoelectrochemical sensor shows excellent selectivity, sensitivity, stability and accuracy for HE4 determination. Experimental conditions including incubation time and pH value for determining HE4 were optimized in this study. The photocurrent variation (Δ I) decreased with increasing HE4 concentration (cHE4) and it was linearly proportional to cHE4 varied from 25 pg mL-1 to 4.0 ng mL-1. The detection limit of the imprinted sensor for determining HE4 was estimated to be 15.4 pg mL-1 (S/N = 3). The imprinted photoelectrochemical sensor was used to determine HE4 in human serum samples accurately