The x‐ray absorption spectra of Ge and of Br in NaBr have been measured to pressures of 52 and 21 kbars, respectively, in a boron carbide and diamond anvil cell in which pressure was measured via the ruby‐fluorescence technique. Although Bragg peaks from the diamond anvil reduced the accuracy, atomic spacings in both materials could be determined by extended x‐ray absorption fine‐structure (EXAFS) analysis. Changes in the nearest‐neighbor separations in NaBr, and Ge to at least 40 kbars, agreed with literature values, indicating that the EXAFS phase shifts are quite insensitive to such pressures. In addition the near‐edge peak positions in the NaBr spectra appeared to readily shift with pressure, which suggests that NaBr may be quite suitable as a pressure standard in future work of this type.