Modern photovoltaic technologies are increasingly evaluated not only in terms of power conversion efficiency and cost, but also with respect to resource origin, toxicity, recyclability, and overall life-cycle impacts. Within this broader sustainability framework, bio-based and bio-inspired materials derived from biomass or mimicking biological structures have emerged as promising candidates for a wide range of photovoltaic components, including active layers, interfacial modifiers, substrates, encapsulants, and natural dyes. This review provides a layer-by-layer overview of such materials implemented or proposed in dye-sensitized, organic, perovskite, biohybrid, and silicon solar cells, linking their molecular structures and optoelectronic properties to representative device performances and key degradation pathways. Cross-cutting challenges related to moisture and thermal stability, barrier performance, feedstock variability, and the risk of “greenwashing” are highlighted, emphasizing that sustainability claims must be supported by quantitative metrics such as life-cycle assessment, circularity indicators, and durability studies. Finally, we outline promising research directions in molecular engineering, hybrid biosynthetic architectures, and advanced encapsulation concepts that could enable bio-based materials to make a meaningful contribution to low-impact photovoltaic technologies.