One of the most important isotopes to be considered for disposal in the proposed UK Geological Disposal Facility (GDF) for higher-activity radioactive wastes will be 99Tc, due to its long half-life, high fission yield and ability to migrate through the geosphere as the pertechnetate ion. Much of the Tc is likely to be in the lower Tc(IV) oxidation state due to the low Eh in the near field. Batch Tc(IV) sorption experiments have been performed from pH 3–13, using 95mTc as a spike, in the presence of quartz, hematite, goethite, plagioclase feldspar, sand and shale. Solutions containing Tc(IV) were prepared at trace concentrations to avoid precipitation of TcO2. Values for the partition coefficient (Rd) were found to range from ∼4 up to ∼2×104 cm3 g−1. Rd was heavily dependent on pH in all cases, with the highest values being found in the circumneutral area. These data will inform the performance assessment for the near-field behaviour of technetium in the UK's planned higher-activity wastes GDF. Surface complexation modelling has been performed, fitting the data using both monodentate and bidentate binding models.