The hard x‐ray spectra of CuO, Cu2O, and pure Cu metal have been measured at x‐ray absorption near‐edge structure (XANES) regions with a photoacoustic detector using synchrotron radiation. It is shown that the information derived from XANES is also included in the x‐ray photoacoustic spectrum which reflects the heat production processes in those copper oxides and metal. However, the results showed that the increases and changes of the photoacoustic signal were different from those of the x‐ray absorption coefficient at the photon energy regions.