A general pathway towards NHC (NHC = N-heterocyclic carbene)-stabilized galliummonotriflates NHC ∙ GaH2(OTf) (NHC = IDipp, 1a; IPr2Me2, 1b; IMes, 1c; IDipp = 1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene, IPr2Me2 = 1,3-bis-(diisopropyl)-4,5-dimethyl-imidazolin-2-ylidene, IMes = 1,3-bis(2,4,6-trimethylphenyl)-imidazolin-2-ylidene) is reported. Quantum chemical calculations give detailed insight into the underlying reaction pathway. The obtained NHC ∙ GaH2(OTf) compounds were employed in reactions with donor-stabilized pnictogenylboranes to synthesize the elusive cationic parent 13/15/13 chain compounds [IDipp ∙ GaH2ER2E'H2 ∙ D][OTf] (3a: D = IDipp, E = P, E' = B, R = H; 3b: D = NMe3, E = P, E' = B, R = H, 3c: D = NMe3, E = P, E' = B, R = Ph, 3d: D = IDipp, E = P, E' = Ga, R = H). Supporting computational studies highlight the electronic features of the products.