Clozapine, an effective antipsychotic drug, was found generating a pair of redox peaks at about 0.33-0.4V (versus SCE) at 16-mercaptohexadecanoic acid (i.e. MHA) self-assembled monolayer (SAM) modified gold electrode (i.e. MHA/Au) in 0.05molL(-1) Tris-HCl (pH 8.1) buffer solution. Sensitive and quantitative measurement of clozapine based on anodic peak was established under optimum conditions. The anodic peak current was linear to clozapine concentration in the range from 1x10(-6) to 5x10(-5)molL(-1) with the detection limit of 7x10(-9)molL(-1). This method was successfully applied to the detection of clozapine in drug tablets and proved to be reliable compared with ultraviolet spectrophotometry (UV). The MHA SAM was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), contact angle goniometry, electrochemical impedance spectroscopy (EIS) and electrochemical probe.