AbstractCoacervation plays an important role in the molecular assembly towards soft materials with a diversity of function (e. g., underwater adhesives of mussels and membraneless organelles). Coacervation is observed when one homogenous solution spontaneously separates into two immiscible liquid phases of low and high solute concentration, also known as liquid‐liquid phase separation (LLPS), which enables spatiotemporally local concentration of specific molecules. LLPS is a common physical phenomenon in aqueous solutions of polyelectrolytes, surfactants and biomolecules, which has been extensively explored for applications in the fields of environmental remediation, cosmetic formulation, protein purification, extractive fermentation and pharmaceutical microencapsulation. This review summarizes the development of LLPS with low molecular weight amphiphiles to construct simple and complex coacervates using conventional surfactants and novel amphiphiles such as azobenzene‐derivatives and peptides. We also highlight the applications of these amphiphile coacervates in the extraction of biomolecules, construction of protocell models and drug delivery.