To fulfil the growing global demand for energy, numerous efforts have been directed towards developing efficient materials for energy storage applications. Lead-free perovskites (LFPs), which has the structural formula ABX3, have emerged as next-generation electrode materials due to their extraordinary conductivity, structural tunability, thermal/chemical stability, excellent ion transport kinetics, and reduced environmental toxicity as compared to their lead-based counterparts and could be employed in various energy storage systems, including supercapacitors, rechargeable batteries, and hybrid devices. Furthermore, their versatile crystal structure allows for compositional modifications that can optimize key performance parameters such as capacity, rate ability, and stability. Thus, this chapter provides a comprehensive overview of LFPs, highlighting their structural and physicochemical properties, and synthesis approaches along with existing challenges and future perspective for developing high-performance and environmentally friendly energy storage devices.