Carbon monoxide (CO) and hydrocarbons (HCs) generally have competitive adsorption on the active site of noble-metal nano-catalysts, thus developing an effective way to reduce the passivation of competitive reaction with each other is an urgent problem. In this study, we successfully synthesized transition metal-noble metal (Pt-M) alloys via introducing inexpensive metal elements (M = Ni, Co and Cu) into Pt particles and then deposited on alumina support to form Pt-based catalysts. Subsequently, we choose CO and toluene as polluting gases to evaluate the catalytic activities of Pt-M/Al2O3 catalysts. Introducing inexpensive metal elements (M = Ni, Co, and Cu) significantly changed the physicochemical properties and catalytic activities of these Pt-based catalysts. It can be found that the Pt-Co/Al2O3 catalyst exhibited outstanding catalytic activity for CO and toluene oxidation under mixed gas atmosphere, compared with other Pt-based catalysts, which is due to the higher dispersity, more surface adsorption oxygen, and well redox ability. Surprisingly, H2O could promote the catalytic activities for CO/toluene co-oxidation over the Pt-Co/Al2O3 catalyst. Thus, the present synthetic strategy not only opens an avenue towards the synthesis of noble metal-based catalysts, but also provides an excellent tolerance to H2O in the catalytic process.