Water-soluble polymers such as poly(acrylic acid) (PAA) are widely applied in dispersants, thickeners, flocculants, and superabsorbent polymers. Here, submicrometer-sized monodisperse PAA particles were successfully prepared by precipitation polymerization in acetonitrile at 55 °C with 2,2'-azobis(2,4-dimethylvaleronitrile) as an initiator. In a medium with a high dielectric constant, the particles were stabilized by electrostatic repulsion without a colloidal stabilizer during the polymerization. Moreover, the obtained PAA particles were spontaneously cross-linked in the absence of a cross-linker. The degree of the cross-linking was strongly dependent on the amount of water (500-10,000 ppm) in the polymerization medium. The PAA particles swelled more with acrylic acid with an increase in the amount of water. Thus, in the case of high water content, the particles would become the main polymerization loci, which in turn results in the cross-linking structures owing to the α-hydrogen abstraction of PAA chains during the polymerization.