Mounting evidence indicates that the nervous system plays a central function in pathogenesis. To study the association of the nervous system in diseases, tools that allow delicate control of neural behavior are crucial. Wireless electrical modulation of neural cells via opto-stimulation is an emerging approach to trigger and control neural behavior. Furthermore, to imitate the highly organized natural neural network, neurite outgrowth needs to be guided to achieve directionality. This work successfully combines bionic fibers with nano-groove topography and evident opto-response to guide neurite outgrowth. With excellent biocompatibility, the bionic opto-responsive fibers spatiotemporally controlled and guided PC12 neurite outgrowth. Transient photocurrent measurement revealed that this effect was attributed to anodic faradaic photocurrents. This bionic opto-responsive fiber has great potential to act as a tool to control and guide neurite outgrowth to study nervous system/disease interaction.