X-ray powder diffraction (XRPD) and Fourier transform infrared (FTIR) spectroscopy are used to characterize the morphology of diacrylate polymer networks, obtained by photoinduced homo- and copolymerizations. XRPD reveals the presence of three sized groups of microgel agglomerates. The dimensions of the microgel agglomerates (D) and the degree of conversion (DC) are explained by the monomer chemical structure, the strength of hydrogen bonds, and relate to selected polymer mechanical properties. The D value increases and the DC decreases as the strength of the hydrogen bonds increases. Copolymerization with monomers lacking groups forming strong hydrogen bonds results in more homogeneous networks with improved mechanical properties.