Supported nanoparticulate Au/Ti-SiO2 catalysts are a promising candidate for selective epoxidation of propene with H2/O2 mixtures. Here, we demonstrate that by altering the acidity of the surface titanol groups in Au/Ti-SiO2, the selectivity of these catalysts in propene oxidation can be controlled. That is, Au/Ti-SiO2 prepared using an alkali base during gold deposition shows basic properties due to the formation of Ti-ONa groups. The catalysts that contained Na+ and neutralized acid sites demonstrate high selectivity toward propene oxide. On the contrary, when the acidity of the Ti-OH groups is preserved by using NH4OH as a base during gold deposition, the catalyst is highly selective toward propanal at a similar propene conversion. This ...