Phase, separation and its kinetics of poly (vinyl methyl ether) (PVME) aqueous solutions was investigated by Rayleigh scattering (RS) technique in this work. Concentration dependence of the lower critical solution temperature and time dependence of phase separation were collected, respectively. The RS spectra revealed the transition of molecular conformation and aggregation of molecular chains in the course of phase separation. It was found that upon heating PVME chains changed from expanded coils to collapsed globules and then aggregated. In contrast, during cooling, the chain aggregates were initially swelled and followed by gradual dissociation, while the conformation of molecular chains finally returned to its original state. By means of Avrami equation and Arrhenius formula, apparent activation energy of phase separation of PVME aqueous solutions was estimated. Moreover, a model was proposed to describe the phase separation process.