GC stationary phases composed of binary mixtures of two polymeric ionic liquids (PILs), namely, poly(1-vinyl-3-hexylimidazolium) bis[(trifluoromethyl)sulfonyl]imide (poly(ViHIm-NTf2))/poly(1-vinyl-3-hexylimidazolium) chloride (poly(ViHIm-Cl)) and poly(1-vinyl-3-hexadecylimidazolium) bis[(trifluoromethyl)sulfonyl]imide (poly(ViHDIm-NTf2))/poly(1-vinyl-3-hexadecylimidazolium) chloride (poly(ViHDIm-Cl)), were evaluated in terms of their on-set bleed temperature and separation selectivity. A total of six neat or binary PIL stationary phases were characterized using the solvation parameter model to investigate the effects of the polymeric cation and anion and PIL composition on the system constants of the resulting stationary phases. The hydrogen bond basicity of the mixed poly(ViHIm-NTf2)/poly(ViHIm-Cl) stationary phases was enriched linearly with the increase in the poly(ViHIm-Cl) content. Results revealed that tuning the composition of the stationary phase allowed for fine control of the retention factors and separation selectivity for alcohols and carboxylic acids as well as selected ketones, aldehydes, and aromatic compounds. A reversal of elution order was observed for particular classes of analytes when the weight percentage of the chloride-based PIL was increased.