Abstract Phosphate sorption at the corundum (α-Al 2 O 3 )/water interface was investigated as a function of phosphate concentration (0.1–1 mM) and pH (3–11) by 31 P solid state NMR spectroscopy, ATR-FTIR, and quantum chemical calculation. The 31 P NMR spectra indicate that under these experimental conditions phosphate adsorbs onto corundum mainly as inner-sphere complexes that yield a peak at δ P = −2.8 ppm with full width at half maximum (FWHM) of 9.2 ppm, with a small amount aluminum phosphate surface precipitates as suggested by an NMR signal observed from δ P = −12 to −20 ppm. We employed 31 P{ 27 Al} rotational echo adiabatic passage double resonance (REAPDOR) to further analyze the phosphate adsorption samples prepared at pH 5 and 9 in order to determine the phosphate/Al coordination. To aid interpretation of the NMR data, a series of bidentate and monodentate structural models of phosphate adsorbed on corundum (0 0 1) and (0 1 2) surfaces were calculated using density function theory (DFT). By comparing the experimental REAPDOR curves and those simulated from these models, we can assign the dominant peaks to bidentate binuclear surface complexes. Formation of bidentate binuclear surface complexes is supported by the ATR/FTIR spectra combined with DFT calculation, which further suggests a mixture of non-protonated bidentate and mono-protonated bidentate surface complexes on the corundum surface at pH 5. At pH 9, both NMR and ATR/FTIR indicate the formation of bidentate surface complexes on corundum surface.