These are electrochemically active materials in their pristine form and have also been utilized to derive various metallic nanostructures such as metal oxides, metal phosphides, metal sulfides, metal borides and carbon encapsulated metals/metal alloys, etc. for electrochemical applications. In recent years, the PB/PBAs and their derivatives have attracted significant interests as novel electrochemical materials for energy storage and conversion applications. Here, we briefly describe the structures of PB/PBAs and their derivatives followed by a comprehensive review on recent studies of their use in electrochemical energy storage (metal-ion batteries, supercapacitors) and conversion (metal-air batteries and water electrolyzers) devices. We not only discuss tuning of their internal chemistry but also compare device performance data among different studies and try to establish correlations between material properties with device performances.