In this paper we carry out a surface study of promising supported solid acid catalysts commonly used for the production of high value chemicals derived from glycerol. In particular, γ, θ and α alumina (Al₂O₃) were modified by (i) grafting with 5 wt% zirconia, (ii) doping with 30 wt% silicotungstic acid (STA), and (iii) using both zirconia and STA. The aim is to rationalise the effect of these different parameters on structural properties and surface adsorption through a comprehensive multi-technique approach, including recently developed NMR relaxation techniques. XRD and laser Raman spectroscopy confirmed a strong interaction between STA and the γ-/θ-Al₂O₃ resulting in a distortion of the supported STA Keggin structure relative to that of bulk STA. Conversely, a much weaker interaction between the supported STA and α-Al₂O₃ was measured. NMR relaxation demonstrated that the STA doping increases the adsorption properties of the catalyst, particularly for γ-/θ-Al₂O₃. For catalysts based on α-Al₂O₃, such effect was negligible. Thermogravimetric/differential thermogravimetry (TGA/DTG) analysis suggested that zirconia-grafted and non-grafted θ-Al₂O₃ and γ-Al₂O₃ are suitable materials for increasing the thermal stability of STA whereas α-Al₂O₃ (both grafted and non-grafted) does not improve the thermal stability of STA.