This review highlights the current research on the interactions between biological cells and Layered Double Hydroxides (LDH). The as‐prepared biohybrid materials appear extremely attractive in diverse fields of application relating to health care, environment and energy production. We describe how thanks to the main features of biological cells and LDH layers, various strategies of assemblies can be carried out for constructing smart biofunctional materials. The interactions between the two components are described with a peculiar attention to the adsorption, biocompatibilization, LDH layer internalization, antifouling and antimicrobial properties. The most significant achievements including authors′ results, involving biological cells and LDH assemblies in waste water treatment, bioremediation and bioenergy generation are specifically addressed.