Merging the functionality of an organic field-effect transistor (OFET) with either a light emission or a photoelectric effect can increase the efficiency of displays or photosensing devices. In this work, we show that an organic semiconductor enables a multifunctional OFET combining electroluminescence (EL) and a photoelectric effect. Specifically, our computational and experimental investigations of a six-ring thiophene-phenylene co-oligomer (TPCO) revealed that this material is promising for OFETs, light-emitting, and photoelectric devices because of the large oscillator strength of the lowest-energy singlet transition, efficient luminescence, pronounced delocalization of the excited state, and balanced charge transport. The fabricated OFETs showed a photoelectric response for wavelengths shorter than 530 nm and simultaneously EL in the transistor channel, with a maximum at ~570 nm. The devices demonstrated an EL external quantum efficiency (EQE) of ~1.4% and a photoelectric responsivity of ~0.7 A W-1, which are among the best values reported for state-of-the-art organic light-emitting transistors and phototransistors, respectively. We anticipate that our results will stimulate the design of efficient materials for multifunctional organic optoelectronic devices and expand the potential applications of organic (opto)electronics.