The reaction of CuSCN (or CuCl2) in the presence of excess KSCN directed by viologen-based linear templates in a dimethyl formamide–methanol system affords six coordination polymers, {(MV)[Cu2(SCN)4]}n (1, MV2+ = 1,1′-dimethyl-4,4′-bipyridinium), {(PrV)[Cu2(SCN)4]}n (2, PrV2+ = 1,1′-dipropyl-4,4′-bipyridinium), {(iPV)[Cu2(SCN)4]}n (3, iPV2+ = 1,1′-diisopropyl-4,4′-bipyridinium), [(1-iBV)Cu2(SCN)3]n (4, 1-iBV2+ = 1-isobutyl-4,4′-bipyridinium), {(iBV)[Cu2(SCN)4]}n (5, iBV2+ = 1,1′-diisobutyl-4,4′-bipyridinium), and {(PtV)[Cu2(SCN)4]}n (6, PtV2+ = 1,1′-dipentyl-4,4′-bipyridinium). The [Cu2(SCN)4]n anion in compounds 1, 3 and 5 adopts an infinite two-dimensional polypseudorotaxane architecture and proved effectively that the stoppers at the end can enhance the polyrotaxane formation in the crystalline state, whereas the anion moieties in compounds 2 and 6 exhibit one-dimensional linear architectures, suggesting dethreading from envelopes once solidifying from solution phase. Compound 4 was found to be a two-dimensional coordination polymer with the organic ligand carrying a single charge. The side chain template effect of substituted group, UV-Vis diffuse reflectance spectra in the solid state and TGA properties of the six complexes are investigated.