A pump-probe photothermal mirror (PTM) method has been developed to determine the thermal diffusivity of opaque solid samples. The method involves the detection of the distortion of a probe beam whose reflection profile is affected by the photoelastic deformation of a polished material surface induced by the absorption of a focused pump field. We have measured the time dependence of the PTM signal of Ti, Al, Cu, Sn, Ag, and Ni samples. We show theoretically and experimentally that the time derivative of the signal in the first microseconds is proportional to the square root of the thermal diffusivity coefficient. The method affords a simple calibration and efficient interpretation of experimental data for a sensitive determination of the thermal diffusivity coefficient for materials. We demonstrate the applicability of the technique by measuring the thermal diffusivities of wadsleyite (β-Mg2SiO4) and diopside (MgCaSi2O6), two important minerals relevant to geophysical studies.