A series of polyurethane (PU)/vinyl ester resin (VER) simultaneous IPNs (interpenetrating polymer networks) with different component ratios and comonomers types introduced to VER were synthesized and the polymerization processes were traced by Fourier transform infrared spectroscopy (FTIR) to study the kinetics of IPNs and hydrogen bonding action within multi-component. Furthermore, the relationship of polymerization process with morphology was investigated in detail for the first time by the morphological information given by chemical action between two networks besides physical entanglement, atomic force microscope (AFM) observation and dynamic mechanical analysis (DMA). The results indicated that the degree of hydrogen bonding (Xb,UT,%). calculated from functional group conversional rate and fine structures gained from FT-IR spectra of two networks, were affected by PU/VER weight ratios and comonomer types of VER. The relationship of formation kinetics and morphology showed that the change of Xb,UT (%) values exhibited excellent consistency with that of phase sizes observed by AFM and detected by DMA. A series of polyurethane (PU) / vinyl ester resin (VER) simultaneous IPNs (interpenetrating polymer networks) with different component ratios and comonomers types introduced to VER were synthesized and the polymerization processes were traced by Fourier transform infrared spectroscopy (FTIR) to study the kinetics of IPNs and hydrogen bonding action within multi-component. Further, the relationship of polymerization process with morphology was investigated in detail for the first time by the morphological information given by chemical action between two networks besides physical entanglement, atomic force microscope (AFM) The results indicated that the degree of hydrogen bonding (Xb, UT,%). calculated from functional group conversional rate and fine structures gained from FT-IR spectra of two networks, were affected by PU / VER weight ratios and comonomer types of VER. The relationship of formation kinetics and morphology showed that the change of Xb, UT (%) values ​​demonstrated excellent consistency with that of phase sizes observed by AFM and detected by DMA.