The GO-COOH/AuNPs/ZnAPTPP nanocomposites were constructed using zinc monoamino porphyrin (ZnAPTPP) through π–π conjugation with carboxylated graphene oxide (GO-COOH) loaded with Au nanoparticles (AuNPs). Prepared materials were characterized by 1H NMR spectra, UV–vis absorption spectroscopy and electrochemical impedance spectroscopy. ITO electrode surface was modified with the prepared nanocomposites showed a good photocurrent response when the bias potential, −0.1V was applied. Nanocomposites modified ITO electrode exhibited good photo-response to the 4-nitrophenol (4-NP). ZnAPTPP were excited from HOMO to LUMO under light irradiation, the photoexcited electrons injected into the conduction band of GO-COOH, and then transferred to AuNPs further to the ITO. The presence of GO-COOH and AuNPs improved the separation of photogenerated charges due to their synergetic effect and excellent conductivity. Externally added 4-NP scavenges the photogenerated holes i.e. it acts as a sacrificial electron donor thereby it enhances the photocurrent of the system. Based on this interaction, a novel method for photoelectrochemical detection of 4-NP was developed with a linear range from 0.1 to 15nmol/L (r = 0.996) and detection limit of 0.04nmol/L (S/N = 3). Proposed method is simple and sensitive and this was successfully applied for the quantification 4-NP in river water sample matrices.