<p>Flexible photoelectric sensors with high stretchability and easy integration have accelerated the evolution of wearable electronic devices. The CNTs (carbon nanotubes)-based composites are a suitable alternative to the preparation of sensing materials by virtue of the remarkable performance. Hitherto, the preparation process aimed at fabricating the versatile flexible photoelectric devices has been constrained due to the poor charge separation and photoelectric conversion efficiency under the circumstance of extension, bending, or folding. Here, we develop a novel technique involving the in situ polymerization and co-precipitation method to prepare the CNT-PAN (CNT-polyaniline) composite and Ga₂O₃, which are deposited on the surface of sensor, respectively, which consisted of the interdigital Au electrode and flexible PDMS substrate. The study manifests the synergetic transformation of the flexibility and photoelectric property. The modification of PAN improves the stretchability and charge transfer capability via the active functional groups on the polyaniline and strong π–π electrons interaction between CNT and PAN. The introduction of Ga₂O₃ enhances the light–matter interaction. On this basis, the CNT-PAN and Ga₂O₃ are deposited on the surface of sensor, respectively, which consisted of the interdigital Au electrode and flexible PDMS substrate for the sake of enhancing the light–matter interaction. The study manifests that photoconductive property was enhanced by the assembly process. The findings provide enlightenment into the exploration of multi-performance optoelectronic devices.</p>