CO2 and toxic wastewater were converted into bioelectricity through photo-bioanode in a microbial fuel cell (MFCs). Photo-bioanode provided multifunctional regions due to four distinct layers: the first layer integrates a Fe-doped graphitic carbon nitride photocatalyst. In contrast, the second layer contains refractory organics (RO) degrading microbes. Sequentially, the third layer consists of CO2-consuming bacteria and the fourth layer accommodates exoelectrogens. The first layer not only generated plentiful electrons upon illumination but also quenched electrons from the inner layers, facilitating the degradation of RO. The second layer transformed RO into ions (NH4, NO3/NO2) and C6H12O6, sequentially transported into the third and fourth layers. Within the third layer, CO2-consuming bacteria utilized CO2 leaked from the exoelectrogenic layer, effectively curbing its accumulation in the fourth layer. Here, exoelectrogens employed ions and C6H12O6 as their energy source, producing an electricity output 1.4 times greater than the benchmark. This synergistic performance yielded a voltage of 2.5 V, a current of 2.8A, and a power yield of 1.98 W/organic loading rate (OLR). Thus, the unique layered structure of the photo-bioanode facilitated the self-development of distinct microbial communities, thereby formulating a multifunctional and highly dynamic system with zero-liquid discharge.