Herein we report on reactions of "imidazoliumyl-transfer" reagents [(LSiMe3)-Si-(R/R')][OTf] (4(R/R')[OTf]); L = imidazolium-2-yl, R/R': Me/Me, Pr-i/Me, Dipp/H, Dipp/Cl) with pnictogen trichlorides PnCl(3) (Pn = P, As, Sb) in various stoichiometries. In the case of the 1:1 reaction of [(LSiMe3)-Si-(R/R')]-[OTf] with PCl3 the corresponding cationic imidazoliumylsubstituted dichlorophosphanes [(LPCl2)-P-(R/R')]+ (1(p)((R/R')))+ are obtained as triflate salts on a multigram scale. We found that the reactions using various stoichiometries of [(LSiMe3)-Si-(R/R')][OTf] and PnCl(3) are less selective in the case of the heavier congeners or by decreasing steric demand of the R-group attached to the N atoms of the heterocycle. An equilibrium between the monocation [(LPCl2)-P-(Me/Me)] (1p((Me/Me)+)), the dication [(L2PCl)-P-(Me/Me)](2+) (2p((Me/Me)2+)), and the trication [I(Me/Me)(3)P](3+) (5p((Me/Me)3+)) is observed in solution. Reactions of the monocationic derivatives [L((R/R'))PnCl(2)][OTf] (Pn P, As) with Me3SiX (X = CN, N-3) resulted in the exchange of the chloro groups for the respective pseudohalogen and yielded the dicyano [L((R/R'))Pn(CN)(2)][OTf] (6(Pn)((R/R'))[OTf]) and diazidosubstituted pnictanes [L((R/R'))Pn(N-3)(2)][OTf] (7(Pn)((R/R')) [OTf]), respectively. All new compounds are thoroughly characterized by multinudear NAIR, IR, and Raman spectroscopy. For most cases the molecular structure was confirmed by X-ray crystal structure analysis.