Flexible thin film solar cells are lightweight and foldable, which exhibit promising applications in outdoor activity and portable equipment. The key challenge lies in the design of flexible photovoltaic materials, including photo absorbers, hole and electron transporting materials, and electrodes. In addition, the design of the device structure could also be an effective approach to achieve high flexibility. This chapter focuses on synthesizing photovoltaic materials, designing microstructures, and optimizing photovoltaic performance for dye-sensitized solar cells, polymer solar cells, and perovskite solar cells. Particularly, the advantages and disadvantages of flexible film solar cells for wearable solar cells will be introduced. For instance, the enhanced flexibility compared with conventional rigid silicon solar cells but the insufficient capability to tolerate complex deformation during practical applications.