Triflate salts of trications [(bipy)₂E]³⁺ ([6E][OTf]₃) and [(tbbipy)₂E]³⁺ ([6′E][OTf]₃) (bipy = 2,2′-bipyridine, tbbipy = 4,4′-di-^tbutyl-2,2′-bipyridine; E = P, As, Sb, Bi) have been synthesized and comprehensively characterized. The unique molecular and electronic structures of this new class of complexes involving pnictogen Lewis acids has been assessed in the solid, solution and gas phases to reveal systematic variations in metric parameters, ligand lability and charge concentration. While the Lewis acidity of E³⁺ has the trend E = Bi < Sb < As < P as determined by gas-phase calculations and ¹H NMR spectroscopy, the Lewis acidity of [6E]³⁺ has the trend E = P < As < Sb < Bi according to gas-phase calculations. Derivatives of [6′E][OTf]₃ (E = P, As) are latent sources of E(OTf)₃ as demonstrated by their reactions with dmap, which give the corresponding derivatives of [(dmap)₃E][OTf]₃. The highly oxidizing nature of P(OTf)₃ and As(OTf)₃ is evidenced in reactions of [6′E][OTf]₃ (E = P, As) with phosphines, which give E^I-containing monocations [(R₃P)₂E]¹⁺ and oxidatively coupled dications [R₃PPR₃]²⁺, illustrating new P–P and P–As bond forming strategies. Cations [6′E]³⁺ (E = P, As) are C–H bond activating agents that dehydrogenate 1,4-cyclohexadiene, with higher activity observed for E = P. Combinations of [6′E]³⁺ and ^tBu₃P activate H₂ and D₂ under mild conditions, evidencing frustrated Lewis pair activity. Oxidation of [6′P][OTf]₃ with SO₂Cl₂ gives [(tbbipy)₂PCl₂][OTf]₃, containing a P^V-trication, but there is no evidence of the analogous reaction with [6′As][OTf]₃. The observations highlight new directions in the chemistry of highly charged cations and reveal a rich reactivity for p-block triflates E(OTf)₃, which can be accessed through derivatives of [6E][OTf]₃ and [6′E][OTf]₃.