Phase separation of binary blends composed of a polystyrene derivative (PS) and poly (vinyl methyl ether) (PVME) with a lower critical solution temperature (LCST) was experimentally induced by two different methods: heating and UV light irradiation. Using laser light scattering combined with the temperature jump (T-jump) technique, it was demonstrated that in the case of heating, the mixture undergoes phase separation via the nucleation-and-growth (NG) and the spinodal decomposition (SN) processes under shallow and deep quenches, respectively. Particularly, the crossover from the spinodal decomposition to the nucleation-and-growth process was observed at long time under a deep T-jump by light-scattering experiments. On the other hand, in the photo-crosslink case, the PS/PVME blends undergo a nucleation-and-growth process upon irradiation with weak light intensity, whereas the mixture exhibits the spinodal decomposition under irradiation with strong light intensity. From the analysis of the light-scattering data obtained for the blends under the photo-crosslink, the kinetic data reveal the suppression of morphologies having large characteristic length scales. This feature clearly differs from the phase separation induced by heating where no mode-suppression process was observed. It was also found that distribution of the characteristic length scales (the regularity) of the morphology becomes narrow as the phase separation proceeds for reacting blends, whereas it becomes broader as the phase separation proceeds by heating, revealing the important roles of reaction in the suppression of fluctuations with long wavelengths. These experimental results establish a method to control the length scales and the regularity of the morphology of polymer blends by chemical reaction.