Physical hydrogels of chitosan in the colloidal domain were obtained in the absence of both cross-linker and toxic organic solvent. The approach was based on a reverse emulsion of a chitosan solution in a Miglyol/Span 80 mixture, generally regarded as safe. Temperature and surfactant concentration were optimized, and the impact of the degree of acetylation (DA) and the molar mass of chitosan was investigated. When chitosan had a DA above 30%, only macroscopic gels were obtained, because of the predominance of attractive Van der Waals forces. The lower the molar mass of chitosan, the better the control over particle size and size distribution, probably as a result of either a reduction in the viscosity of the internal aqueous phase or an increase in the disentanglement of the polymer chain during the process. After extraction and redispersion of the colloid in an ammonium acetate buffer, the composition of the particles was around 80% of pure chitosan corresponding to a recovery of 60% of the original input. These new and safe colloids offer wide perspectives of development in further applications.