Density functional theory (DFT) is employed to investigate the promotion of B(C6F5)3as a ligand for titanium (or vanadium) catalysts in ethylene/1-hexene copolymerization reactions. The results reveal that (I) Ethylene insertion intoTiB(with B(C6F5)3as a ligand ) is preferred overTiH,both thermodynamically and kinetically. (II) InTiHandTiBcatalysts, the 2,1 insertion reaction (TiH21andTiB21) is the primary pathway for 1-hexene insertion. Furthermore, the 1-hexene insertion reaction forTiB21is favored overTiH21and is easier to perform. Consequently, the entire ethylene and 1-hexene insertion reaction proceeds smoothly using theTiBcatalyst to yield the final product. (III) Analogous to theTicatalyst case,VB(with B(C6F5)3as a ligand) is preferred overVHfor the entire ethylene/1-hexene copolymerization reaction. Moreover,VBexhibits higher reaction activity thanTiB, thus agreeing with experimental results. Additionally, the electron localization function and global reactivity index analysis indicate that titanium (or vanadium) catalysts with B(C6F5)3as a ligand exhibit higher reactivity. Investigating the promotion of B(C6F5)3as a ligand for titanium (or vanadium) catalysts in ethylene/1-hexene copolymerization reactions will aid in designing novel catalysts and lead to more cost-effective polymerization production methods.