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The hard x‐ray photoacoustic signal intensities of copper have been measured at an x‐ray absorption near‐edge structure (XANES) region as functions of sample thickness (from 5 to 300 μm) and modulation frequency (from 5 to 50 Hz). It is shown that the photoacoustic signal intensities show maxima at the sample thickness close to 10 μm for each modulation frequency. The x‐ray photoacoustic signal varies from f-1.0 ( f denotes modulation frequency) up to 20 μm sample thickness, whereas it varies from f-0.5 beyond a 20 μm sample thickness, which is not consistent with the Rosencwaig–Gersho theory for the photoacoustic effect in solids.