A simple method has been proposed for the removal of diffraction peaks from x‐ray absorption fine structure spectra of a single crystal observed in the fluorescence mode (i.e., excitation spectrum), in which the diffraction peaks inevitably appear. With a patching up of the appropriate spectrum regions from the spectra having many diffraction peaks, it is shown that we can synthesize one spectrum without the diffraction peaks. Here, several spectra are observed in rotating the single crystal within small angles. As an example, this method is successfully applied in finding the local structure around the Cr3+ion in a single crystal of &agr;‐Al2O3:Cr3+. The bond distances of Cr3+–O2−have been determined asr1=2.04 A˚ andr2=1.95 A˚, those are closer to the bond distances in Cr2O3.