Spontaneous vesicles form in aqueous solutions of mixtures of cationic and anionic surfactants. Here we report that vesicles are also found in systems containing a polymerizable monomer as a fourth component and that these vesicles can be polymerized with retention of the equilibrium structure. This is a convenient and versatile approach in which the vesicle architecture can be controlled by equilibrium surfactant self-assembly prior to polymerization, while the microstructure of the spherical polymer network can be controlled by the choice of monomer and degree of cross-linking.