The explore and development of electrocatalysts have gained significant attention due to their indispensable status in energy storage and conversion systems, such as fuel cells, metal–air batteries and solar water splitting cells. Layered double hydroxides (LDHs) and their derivatives (e.g., transition metal alloys, oxides, sulfides, nitrides and phosphides) have been adopted as catalysts for various electrochemical reactions, such as oxygen reduction, oxygen evolution, hydrogen evolution, and CO2 reduction, which show excellent activity and remarkable durability in electrocatalytic process. In this review, the synthesis strategies, structural characters and electrochemical performances for the LDHs and their derivatives are described. In addition, we also discussed the effect of electronic and geometry structures to their electrocatalytic activity. The further development of high-performance electrocatalysts based on LDHs and their derivatives is covered by both a short summary and future outlook from the viewpoint of the material design and practical application.