The data are related to material characterisation of silica-supported sulfonic acid catalysts (including TEM, XRD, N2 porosimetry, DRIFTS, XPS, TGA, pyridine adsorption/DRIFTS, propylamine adsorption/TGA-MS), and catalytic esterification of model molecules and real bio-oil. The experimental protocols are described in details in the electronic supporting information (ESI) associated with this article. This will be available online on ChemSusChem website free of charge. These data were collected and analysed in order to investigate the impact of macroporosity on catalytic upgrading of fast pyrolysis bio-oil by esterification over silica sulfonic acids.