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Electrochemical molecularly imprinted polymers (e-MIPs) were grafted for the first time as a thin layer to the surface of a gold electrode to perform trace level electroanalysis of benzo(a)pyrene (BaP). This was achieved by controlled/living radical photopolymerization of a redox tracer monomer (ferrocenylmethyl methacrylate, FcMMA) with ethylene glycol dimethacrylate in the presence of benzo(a)pyrene as the template molecule. For that purpose, a novel photoiniferter-derived SAM was first deposited on the gold surface. The SAM formation was monitored by cyclic voltammetry and electrochemical impedance spectroscopy. Then, the “grafting from” of the e-MIP was achieved upon photoirradiation during a controlled time. Differential pulse voltammetry was used to quantify BaP in aqueous solution by following the modification of the signal of FcMMA. A limit of detection of 0.19 nM in water and a linear range of 0.66 nM to 4.30 nM, were determined, thus validating the enhancement of sensitivity induced by the close contact between the e-MIP and the electrode, and the improved transfer electron.