In‐office products containing oxalates have been claimed to be clinically effective in reducing dentine sensitivity, although there has been limited supporting clinical data. The rationale for their use appears to be based on their potential to act as occluding and/or nerve desensitizing agents. Four commercially available oxalate‐containing products were applied to etched dentine discs and the extent of tubule occlusion was observed by scanning electron microscopy. Tenure Quick (aluminium oxalate), Sensodyne Sealant (ferric oxalate) and MS Coat (oxalic acid) covered the dentine surface and occluded the tubules. However, Butler Protect (potassium oxalate) did not cover the surface to any great extent but provided some occlusion. The presence of oxalates after application to glass slides and dentine discs was examined using thin film X‐ray diffraction. From samples on glass, only potassium oxalate could be clearly identified (JCPDS 14‐0845). No oxalate was detected on dentine discs in either thin film geometry or standard theta two theta mode. We have demonstrated that professionally applied in‐office products containing oxalate are capable of covering the dentine surface and/or occluding the tubules to varying degrees. However, X‐ray diffraction analysis was unable to confirm the oxalate profile for all products as described in the available commercial literature.