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The series of heterodinuclear metal oxide carbonyls in the form ofTaNiO(CO)n-(n =5-8) are generated in the pulsed-laser vaporization source and characterized by mass-selected photoelectron velocity-map spectroscopy.During the consecutive CO adsorption,the μ2-O-bent structure initially is the most favorable for TaNiO(CO)5,and subsequently both μ2-O-bent and μ2-O-linear structures are degenerate for TaNiO(CO)6,then the μ2-O-linear structure is most preferential for TaNiO(CO)7_ and finally the η2-CO2-tagged structure is the most energetically competitive one for TaNiO(CO)8,i.e.,the CO oxidation occurs at n=8.In contrast to the literature reported CO oxidation on heteronuclear metal oxide complexes generally proceeding via Langmuir-Hinshelwood-like mechanism,complementary theoretical calculations suggest that both Langmuir-Hinshelwood-like and Eley-Rideal-like mechanisms prevail for the CO oxidation reaction on TaNiO(CO)8-complex.Our findings provide new insight into the composition-selective mechanism of CO oxidation on heteronuclear metal complexes,of which the composition be tailored to fulfill the desired chemical behaviors.