This study has established a robust and straightforward method for the fabrication of uniform poly(vinylamine) hydrogel capsules without using templates that combines the dispersion polymerization and the sequential hydrolysis/cross-linking. The particle sizes are determined by the degree of cross-linking as well as by the cross-linking reaction time, while the shell thickness is independent of these variables. Diffusion-limited reactions occur at the periphery of the particles, leading to the formation of hydrogel shells with a constant thickness. The treatment of the surfaces of hollow hydrogel capsules with oppositely charged biopolymers limits the permeability through the shell of species even with low molecular weights less than 400 g/mol. Furthermore, we demonstrated that the hydrogel shell phase decorated with Au nanoparticles can be optically ruptured by exposure to laser pulse, a feature that has potential uses in optically responsive drug delivery.