We report herein a theoretical study of the reaction of acetaldehyde with Ni+ as an extension of our two recent papers on the decarbonylation of acetaldehyde by late first-row transition metal ions [Zhao, Zhang, Guo, Wu, Lu Chem. Phys. Lett. 2005, 414, 28; Zhao, Guo, Zhang, Wu, Lu ChemPhysChem 2006, 7, 1345]. Geometries of all the stationary points involved in the reaction have been fully optimized at the B3LYP/6-311+G(2df,2pd) level and the decarbonylation mechanism is analyzed in terms of the topology of potential energy surface. Combining with the previous studies, it is found that for the Cr+, Co+, and 4Fe+ mediated systems decarbonylation of CH3CHO only takes place via C-C activation, and aldehyde C-H activation is unlikely to be important, whereas both C-C and aldehyde C-H activations by Ni+ and 6Fe+ could result in the decarbonylation of CH3CHO, where hydride-containing species M+(H)(CO)(CH3) is found to be a common minimum along the reaction pathways.