During changing process of internal structure in a material, the variation of the thermophysical properties reflects the structural change, and at the same time, it can control heat transport in the material. Therefore, real-time information in the form of successive data on thermophysical properties is very important for material processing. We have developed the forced Rayleigh scattering method (FRSM) to apply a real-time monitoring system for the thermal diffusivity in non-invasive manner. In the present study, we have attempted to monitor the dynamic behavior of the thermal diffusivity for a thermally responsive polymer. From the results of continual measurements in the course of conformational change, it is demonstrated that the FRSM has a pretty potential for real-time monitoring system of a material even undergoing a transient process.