Epoxies are inherently brittle materials and to overcome this brittleness, a second microphase (i.e., thermoplastic) is typically added. This modification of epoxy resin using thermoplastics results in reaction-induced phase separating morphologies in the micrometer range. In this study, the influence of the curing history, beyond phase separation, on the interphase formation and final morphology of PEI and the high Tg epoxy system is investigated. Several cure cycles were examined, each with a first dwell temperature ranging from 120 to 180 °C for a given time up to the onset of phase separation (OPS) or up to the 80% degree of cure (80% DOC) and then with a second dwell at 200 °C for 20 min to complete the cure cycle. Hot-stage microscopy experiments were carried out at several first dwell temperatures before final conversion at the second dwell. The morphologies and resulting droplet size distribution at the interphase, after the final cure, were analyzed through scanning electron microscopy. Results showed that the diffusion distance was significantly higher in the case of OPS as compared to the 80% DOC case, particularly at lower first dwell temperatures. This behavior was attributed to the fact that, in the case of OPS, polymeric chains were still in a mobile state and diffused further during the second dwell curing stage, while at 80% DOC, polymeric chains were completely bound but still diffuse due to non-stoichiometric curing. This restricted mobility of polymeric chains after phase separation (80% DOC) resulted in a larger number of smaller droplets as compared to the OPS case.