A novel method for the synthesis of the homogeneous homoleptic cationic tantalum(V)tetramethyl complex [(TaMe4)+ MeB(C6F5)3−] from neutral tantalumpentamethyl (TaMe5) has been described, by direct demethylation using B(C6F5)3 reagent. The aforesaid higher valent cationic tantalum complex was characterized precisely by liquid state 1H-NMR, 13C-NMR, and 1H-13C-NMR correlation spectroscopy.