Millimeter-sized highly spherical poly(amic acid) (PAA) capsules were prepared by curing an emulsion containing non-volatile N,N-dimethylacetamide (DMAc). Although the sphericity of the capsules (> 99%) obtained by the emulsion method was slightly lower than that of corresponding polystyrene capsules, their surface was smooth. The curing conditions to achieve the highest degree of sphericity require stabilization and deformation, which were governed by parameters, such as PAA concentration, the viscosity of the emulsion matrix, stirring speed, and temperature.