Fatty acid vesicles are a kind of natural biological material, which have the advantages of good biocompatibility, low cost and easy self‐assembly in aqueous solution. However, vesicles formed of fatty acids have weak pH stability and thermostability, and poor divalent salt resistance, which limit their applications. In this work, the anionic surfactant sodium oleate and the polysaccharide carboxymethylcellulose sodium were mixed to form composite vesicles in a wide pH range, which can be close to the pH range of the physiological environment. The morphology of the composite vesicles was characterized using transmission electron microscopy and the particle size was determined by dynamic light scattering. Forces and aggregation behavior in the formation of the composite vesicles were investigated using surface tension and Fourier transform infrared observations combined with turbidity measurements. The composite vesicles were used to encapsulate nicotinamide. The encapsulation efficiency and sustained release behavior of nicotinamide loaded in the composite vesicles were evaluated. These results can provide theoretical guidance for the application of drug‐loaded vesicles in cosmetics. © 2021 Society of Industrial Chemistry.