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A modified technique of scanning electron-acoustic microscopy is employed to determine thermal diffusivity of materials. Using the dependence of the electron-acoustic signal on modulation frequency of the electron beam,the thermal diffusivity of materials is characterized based on a simplified thermoelastic theory. The thermal diffusivities of several metals characterized by the modified scanning electron-acoustic microscopy are in good agreement with the referential values of the corresponding materials, which proves that the scanning electronacoustic microscopy can be used to characterize the thermal diffusivity of materials effectively. In addition, for micro-inhomogeneous materials, such as biological tissues, the macro-effective (average) thermal diffusivities are characterized by the technique.