Density functional theory (DFT) methods including LC-ωPBE, CAM-B3LYP, B3LYP, and B3LYP-D3, combined with double Zeta all-electron DZVP basis set, have been employed to conduct computational investigations on nickel-mediated reaction of o-carboranylzirconacycle, n-hexene, and 2-bromophenyltrimethylsilylacetylene in toluene solution. A multistep mechanism leading to the C,C,B-substituted carborane-fused tricyclics, including (1) sequential insertion of alkene and alkyne into Ni–C bonds; (2) double 1,2-migration of the TMS group; (3) B–H activation assisted by Cs2CO3 additive; and (4) reduction cage B–C (sp2) coupling, was proposed. Among these steps, the B–H activation of o-carborane was located as rate-determining step (RDS). With assistance of Cs2CO3 additive (replaced by K2CO3 in simulation), the RDS free-energy barrier at PCM-LC-ωPBE/DZVP level was calculated to be 23.1–23.9 kcal·mol−1, transferring to a half-life of 3.9–15.1 h at 298 K. The predicted half-life coincides well with 80% experimental yields of C,C,B-substituted carborane-fused tricyclics after 12 h. Kinetic data obtained by employing LC-ωPBE method also reproduced the experimental diastereoselective ratio well. Various B–H activation pathways with and without Cs2CO3 additive were taken into consideration, which illustrates Cs2CO3 as an essential guarantee for smooth occurrence of this reaction at room temperature.