Microcrystalline cellulose (MCC), a renewable and sustainable biopolymer derived from natural cellulose, has emerged as one of the most promising material for advancing solar cell technologies. Its unique physicochemical properties, including high thermal stability, biocompatibility, and tunable surface characteristics, make it a versatile component in the development of next-generation photovoltaic systems. The current review offers an in-depth analysis of MCC's role in revolutionizing solar energy applications, particularly its integration into first-, second-, and third-generation solar cells. The focus extends to its use in various photovoltaic architectures, such as traditional organic photovoltaics (OPVs), bulk heterojunction (BHJ) cells, organic-inorganic hybrid solar cells, perovskite solar cells (PSCs), and dye-sensitized solar cells (DSSCs). The review highlights recent advancements in the utilization of MCC for improvement in power conversion efficiency, stability, and environmental sustainability of solar devices. In the present work, we also explore the detailed exploration in MCC and advanced materials, such as nanostructures and polymers, to enhance the light harvesting and charge transportation. Additionally, the discussion addresses critical challenges, including large-scale production, material compatibility, and long-term stability, while proposing the potential research directions. By evaluating MCC's transformative impact on the solar technologies, the review underscores its potential to contribute to a cleaner, more sustainable energy resource in the near future.