A new method of measuring the thermal diffusivity of thin layers has been developed and applied to the characterization of laminated structures. The thermal diffusivity is measured using pyroelectric detection of a laser generated thermal pulse propagating through the sample. The shape of this pulse is governed by the thermal properties of both the sample and the detector. However, the thermal diffusivity of the sample can be determined from the position of the peak in the pyroelectric signal and the sample thickness. This method can be applied to thermal diffusivity measurements of thin or thick films, laminates, and thermal greases.