Organic electrochemical transistors with signal amplification and good stability are expected to play a more important role in the detection of environmental pollutants. However, the bias voltage at the gate may have an effect on the activity of vulnerable biomolecules. In this work, a novel organic photoelectrochemical transistor (OPECT) aptamer biosensor was developed for di(2-ethylhexyl) phthalate (DEHP) detection by combining photoelectrochemical analysis with an organic electrochemical transistor, where MXene/Bi 2 S 3 /CdIn 2 S 4 was employed as a photoactive material, target-dependent DNA hybridization chain reaction was used as a signal amplification unit, and Ru(NH 3 ) 63+ was selected as a signal enhancement molecule. The poly(3,4ethylenedioxythiophene):poly(styrenesulfonate)-based OPECT biosensor modulated by the MXene/Bi 2 S 3 /CdIn 2 S 4 photosensitive material achieved a high current gain of nearly a thousand times at zero bias voltage. The developed signal-on OPECT sensing platform realized sensitive and specific detection of DEHP, with a detection range of 1−200 pM and a minimum detection limit of 0.24 pM under optimized experimental conditions, and its application to real water samples was also evaluated with satisfactory results. Hence, the construction of this OPECT biosensing platform not only provides a promising tool for the detection of DEHP but also reveals the great potential of the OPECT application for the detection of other environmental toxins.