A new and simple photoelectrochemical (PEC) sensor using a glassy carbon electrode (GCE) modified with bismuth vanadate (BiVO4) nanoparticles and dihexadecyl phosphate (DHP) film was useful for acetaminophen (AC) determination. In 0.2 mol L−1 phosphate buffer (pH=9), the GCE without modification exhibited the smaller photocurrent (0.86 μA) when compared with GCE modified with 1.0 mg mL−1 or 2.0 mg mL−1 BiVO4 nanoparticles suspension (5.9 and 34 μA, respectively). Based on the photocurrent signal generated through the interaction between GCE, BiVO4 and the energy of visible light a chronoamperometric method for AC determination was developed. The AC linear range concentration from 0.099 to 0.99 μmol L−1 and limits of detection and quantification of 0.027 and 0.091 μmol L−1, respectively, was obtained. The proposed method was applied to the AC determination in commercial drugs and tap water with satisfactory accuracy and precision. Moreover, the PEC construction was easy and had a short response time, which might confer higher sample throughput for the method.