Polyvinylamine hydrogels with silica particles encapsulated (PVAm/silica) were produced by a two-step synthesis. In the first step, polyvinylformamide/silica (PVFA/silica) hybrids were synthesized from vinylformamide (VFA) and 1,3-divinylimidazolidin-2-one (1,3-bisvinylethyleneurea, BVU), as the crosslinker, by radical copolymerization in silica/water suspensions using different compositions of VFA/BVU. The target product PVAm/silica was obtained by acidic hydrolysis of the PVFA/silica hydrogels in a second step. The chemical structures of both hydrogels, PVFA/silica and PVAm/silica, respectively, were revealed by solid-state C-13(H-1) cross-polarity/magic-angle spinning NMR spectroscopy. Both hydrogels swelled significantly in water. The swelling capacity of the two systems was characterized by the correlation length (or hydrodynamic blob size) of the network meshes with small-angle neutron scattering experiments. is significantly larger for PVAm/silica than for PVFA/silica, which corresponds to the observed higher swelling capacity of this polyelectrolyte material. Furthermore, the swelling behavior of the hybrid hydrogels was quantitatively described in terms of free swell capacity, centrifuge-retention capacity, adsorption against pressure, and free swell rate as compared with values of the corresponding copolymer hydrogels.