In this study the photo-response behaviour of Au/TiO2 systems in the preferential CO oxidation in a H2-rich stream (CO-PROX) was investigated by the first time under simulated solar light irradiation at room temperature and atmospheric pressure. Au nanoparticles, with an average size of 2–5nm, were precipitated-deposited on a mesoporous TiO2, previously synthesized by sol-gel type procedure and thermally treated at different temperatures to obtain anatase/rutile mixed phases. Structural, chemical and optical properties were studied by means of AAS, N2 physisorption, XRD, HR-TEM, DRUV–vis and XPS, investigating the effects of TiO2 polymorphs (anatase, rutile and combination thereof). All samples, containing a very low amount of noble metal (0.5wt%), resulted very active in the photocatalytic CO-PROX at ambient conditions, attaining very high CO conversion and CO2 selectivity values. The Au/TiO2 sample containing both anatase/rutile polymorphs in the support displayed the highest activity, both in dark and under simulated solar light, due to the simultaneous presence of these two titania crystalline phases, capable to lower the effective band gap of the composite system (2.90eV) and improving the photocatalytic activity in the studied reaction. This kind of materials may provide a sustainable and feasible approach to selectively oxidize CO in H2-rich stream under solar light irradiation and ambient conditions.