<p>The fast growth of solar technologies has added to the urge to find the photovoltaic materials and device configurations that can surpass the limitations of the traditional silicon-based systems. This review discusses the emerging solar cell materials, such as perovskites, organic and dye-sensitized systems, quantum dots, carbon-based materials, kesterites, two-dimensional materials, and III-V semiconductors, along with the process of their synthesis, properties of their operation, and the opportunities of their application. Major issues concerning thermal and mechanical stability, moisture and ultraviolet (UV) sensitivity, durability, environmental impact and scalability to large areas are issues of crucial discussion. The paper points out that efficiency will not be enough to determine the future of photovoltaic technologies. The unpredictability of the solar irradiation and decentralization and off-grid approaches to solar energy demand the inclusion of compatible energy storage technologies to guarantee reliability and consistent energy supply. This contribution by combined evaluation of the new photovoltaic materials and energies storage systems emphasizes the stability, manufacturability, recyclability, and system-level integration as control tools in defining the long-term performance. The further development of photovoltaic technologies will be determined by the combined ecosystem of materials, device structures, and the energy storage systems instead of a breakthrough with one material. The article is a synthesized perspective on the next-generation solar materials and the challenges associated with them and can be used as a reference framework that defines sustainable and scalable solar energy systems.</p>