This chapter aims at providing an overview of the potential of layered double hydroxides (LDHs) or hydrotalcite-like compounds (HTs) for contributing to the catalysis of the synthesis of biodiesel through the transesterification of triglycerides. First, the main methods of preparation of HTs and the most relevantfeatures of these materials are presented, with emphasis on their basic properties. Afterwards, the literature on the use of HTs as catalysts, catalysts precursors, and supports of transesterification catalysts is reviewed. HTs are promising materials for the synthesis of biodiesel from refined and waste vegetable oils, showing reasonable resistance to water and free fatty acids but an improvement of the chemical stability under the desired reaction conditions is still necessary.