The viscoelastic and mechanical properties and the morphology of polyurethane (PUR)/polystyrene (PS) interpenetrating polymer networks (IPNs) containing ionic groups have been investigated. Dynamic mechanical thermal analysis (DMTA) revealed a pronounced change in the viscoelastic properties upon the introduction of ionic groups. For the 70 : 30 and 60 : 40 PUR/PS IPN compositions, the DMTA data changed from a dominant PUR to a dominant PS loss factor peak. Higher intertransition loss factor values indicated a significant improvement of IPN component mixing with increasing ionic content. The stress at break values increased only moderately, whereas sharp rises in Young＇s modulus and hardness values were found at 2 wt % ionic groups. At the same time, the strain at break values decreased by half. Scanning and transmission electron microscopy (TEM) indicated a grossly phase-separated morphology for the 70 : 30 PUR/PS IPN without ionic groups. With increasing methacrylic acid (MAA) content, the PS phase domain sizes decreased. At 2 wt % of ionic groups, a TEM micrograph showed interconnected PS phase domains resembling a network structure.