A general pathway towards NHC (NHC=N-heterocyclic carbene)-stabilized galliummonotriflates NHC center dot GaH2(OTf) (NHC=IDipp, 1 a; IPr2Me2, 1 b; IMes, 1 c; 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 center dot GaH2(OTf) compounds were employed in reactions with donor-stabilized pnictogenylboranes to synthesize the elusive cationic parent 13/15/13 chain compounds [IDipp center dot GaH2ER2E'H-2 center dot D][OTf] (3 a: D=IDipp, E=P, E'=B, R=H; 3 b: D=NMe3, E=P, E'=B, R=H, 3 c: D=NMe3, E=P, E'=B, R=Ph, 3 d: D=IDipp, E=P, E'=Ga, R=H). Supporting computational studies highlight the electronic features of the products.