Cathodic photoelectrochemical (PEC) bioassay is more resistant to reductive interferents, and development of high-performance photocathode is imperatively required in precise monitoring target in complex matrices. In this work, a plasmonic Au activated amorphous MoSx photocathode (a-MoSx/Au) was fabricated by sequential electrodeposition. Coupled with a sensitization amplification strategy induced by target-aptamer recognition, an ultrasensitive and high-affinitive signal-on cathodic PEC aptasensor for insulin detection was developed. Under optimum conditions, the sensor exhibits a wide linear range (0.1 pg/mL~100 ng/mL) and an ultralow detection limit (28 fg/mL) even lower than most sensors reported so far. Plasmonic Au activation and target-induced sensitization effect are responsible for high-performance PEC aptasensing of insulin at a-MoSx photocathode.