Detection of chlorpyrifos (CPF) using a surface plasmon resonance (SPR)-enhanced photoelectrochemical sensing system is demonstrated in this study. The presence of CPF was detected based on an increase in the short-circuit photocurrent when a sample is injected into the electrolyte at different concentrations. The short-circuit photocurrent signal was enhanced by both localized SPR of the gold nanoparticles and by the effects of grating-coupled propagating SPR. Using the hybrid SPR-enhancement system, CPF detection was achieved at concentrations as low as 7.5 nM. The proposed technique of leveraging a multifunctional photovoltaic effect can be used for a variety of sensing applications.