In pursuit of a renewable, inexpensive, sustainable, and compact energy source to replace fossil fuels, solar photovoltaic devices have become an ideal alternative to meet human needs for environmentally friendly, affordable, and portable power sources. It is due to their excellent mechanical robustness and outstanding energy conversion efficiency. Concerning the increasing demand for flexible and wearable electronic devices with standalone power sources, much attention has been paid to photovoltaics' flexibility and lightweight developments. Along with high mechanical flexibility and lightweight, flexible photovoltaic devices have the advantages of conformability, bendability, wearability, moldability, and roll‐to‐roll processing into complex shapes that can produce niche products. Emerging solar cells, among other photovoltaic technologies, have been exalted for their high conversion efficiency, low cost, and ease of production, making them a viable new‐generation photovoltaic technology. The main commercialization choice for cutting‐edge solar cells is flexible dye‐sensitized and perovskite solar cells since they can be made using a roll‐to‐roll printing technique and are appropriate for mass manufacturing. More significantly, flexible evolving solar cells may be created on ultrathin and light substrates to fulfill the demands of the developing flexible electronics industry and discover uses that are not possible with traditional photovoltaic technology. In any flexible device, the substrate is a backbone on which further materials rely. A flexible substrate reduces the installation and transportation charges, thereby reducing the system price and increasing power conversion efficiency. In this review, we comprehensively assess relevant materials suitable for making flexible photovoltaic devices. Several flexible substrate materials, including ultra‐thin glass, metal foils, and various types of polymer materials, have been considered. For conducting materials, transparent conducting oxides, metal nanowires/grids, carbon nanomaterials, and conducting polymers have also been comprehended. Progress on various flexible foils, fabrication and stability issues, current challenges, and solutions to those challenges of using conductive polymer substrate is endorsed and reviewed in detail. The originality of this holistic study lies in its ability to offer a thorough overview of recent advancements in flexible dye‐sensitized and perovskite solar cells on polymer substrates, which is conceivable and worthy as a roadmap for future research work.