Electrical signals are a key factor to promote nerve cell neurogenesis. However, the traditionally used exogenous electrical stimulus mode requires additional equipment and complicated wiring, which is very inconvenient. To date, it has been challenging to provide electrical signals to nerve cells in a non-invasive and wireless controllable way, accompanied by the construction of a biomimetic cell microenvironment for supporting nerve cell survival and functional expression. Herein, a new concept of a light-powered oriented bioactive scaffold for remote and wireless electrical stimulation has been developed. By combining electrospinning and electrospraying, the highly oriented polycaprolactone (PCL) microfibrous scaffold with co-sprayed bioactive collagen and photoelectric poly-3-hexylthiophene nanoparticles (P3HT NPs) was obtained, named as PCL-P3HT-Col, which exhibits a considerable photoelectric effect and vital characteristics of the native nerve extracellular matrix. The results show that a photocurrent ranging from 20-80 pA was obtained by changing the light density of a 530 nm green light source. Further, the specific photoelectric conversion effect trigged by the P3HT NPs promotes the oriented elongation and up-regulation of neuronal characteristic factors in rat pheochromocytoma cells (PC12 cells), which is controlled by L-type voltage-gated calcium channel (L-VGCC) activity. This study provides new insights to engineer self-powered scaffolds towards the non-invasive and wireless-controlled stimulation mode of a variety of cells and tissues.