Phase separation behavior and morphology of polymer blends induced by photopolymerization have been investigated in a binary blend of photocurable polymer (2,2-bis(4-(acryloxy diethoxy)phenyl)propane; BPE4) and linear polymer (polysulfone; PSU) using electron microscopy techniques. A ternary phase diagram of mono-BPE4/poly-BPE4/PSU exhibits a lower critical solution temperature (LOST) behavior. In situ polymerization of BPE4 over a wide range of PSU compositions (5-70 wt%) results in network-like bicontinuous phase separated structures at high temperatures, while semi-interpenetrating polymer network (IPN) structures are cured at low temperatures. Even at 10 wt% PSU, the PSU-rich phase is a continuous network-like phase. BPE4-rich domains in the network-like structures are controlled from the nanoscale (30 nm) to the microscale (1 mum) by varying the composition, curing temperature and irradiation intensity. By means of time-evolution study of the phase structure, it is found that BPE4-rich domains appeared in a PSU-rich matrix after the induction time. These domains quickly grow in size up to the sub-micron level, but further growth appears to be slow. The PSU-rich matrix develops into the network-like pattern by the increase in the number and growth of the BPE4-rich domains.