Chitosan colloidal systems, created by dispersing in aqueous solutions of hydrochloric acid, with and without the addition of disodium β-glycerophosphate (β-NaGP), were prepared for the investigation of forming mechanisms of chitosan hydrogels. Three types of chitosan were used in varying molecular weights. The impacts of the charge and shape of the macromolecules on the phase transition process were assessed. The chitosan system without the addition of β-NaGP was characterized by stiff and entangled molecules, in contrast to the chitosan system with the addition of β-NaGP, wherein the molecules adopt a more flexible and disentangled form. Differences in molecules shapes were confirmed using the Zeta potential and thixotropy experiments. The chitosan system without β-NaGP revealed a rapid nature of phase transition—consistent with diffusion-limited aggregation (DLA). The chitosan system with β-NaGP revealed a two-step nature of phase transition, wherein the first step was consistent with reaction-limited aggregation (RLA), while the second step complied with diffusion-limited aggregation (DLA).