This paper explores the potential of biophotovoltaic devices (BPVs) as a sustainable solution for addressing the global energy crisis and combating climate change. BPVs harness renewable electricity from sunlight and water through the photosynthetic activity of microorganisms, such as cyanobacteria and algae, serving as living photocatalysts. The focus is primarily on enhancing photocurrent outputs by developing efficient anode materials. Carbon‐based electrodes, particularly graphene, have emerged as promising candidates due to their cost‐effectiveness, electrical conductivity, and mechanical strength. Despite reduced graphene oxide (RGO) being commonly used, unoxidized graphene has not been extensively explored until recent research demonstrating its excellent current harvesting capacities. Additionally, one‐dimensional structured nanomaterials, such as electrospun nanofibers, have shown potential in promoting electron transport and enhancing charge collection efficiency. An innovative photoanode design is introduced, utilizing cyanobacteria immobilized on a cellulose‐acetate/graphene (CA/Gr) electrospun mat, offering a porous structure conducive to cyanobacterial attachment and efficient electron transfer. A complementary cathode structure, employing aniline‐modified Pt nanoparticles, facilitates the reduction of protons to yield hydrogen gas. Overall, this study highlights BPVs’ potential as a viable clean energy technology and presents novel approaches to enhance their efficiency and sustainability.This article is protected by copyright. All rights reserved.