A family of one-dimensional coordination polymers, [Ag₄(O₂C(CF₂)₂CF₃)₄(phenazine)₂(arene)_n]·m(arene),1(arene = toluene or xylene), have been synthesized and crystallographically characterized. Arene guest loss invokes structural transformations to yield a pair of polymorphic coordination polymers [Ag₄(O₂C(CF₂)₂CF₃)₄(phenazine)₂],2aand/or2b, with one- and two-dimensional architectures, respectively. The role of pre-organization of the polymer chains of1in the selectivity for formation of either polymorph is explored, and the templating effect of toluene andp-xylene overo-xylene orm-xylene in the formation of arene-containing architecture1is also demonstrated. The formation of arene-free phase2b, not accessible in a phase-pure form through other means, is shown to be the sole product of loss of toluene from1-tol·tol[Ag₄(O₂C(CF₂)₂CF₃)₄(phenazine)₂(toluene)]·2(toluene), a phase containing toluene coordinated to Ag(I) in an unusual μ:η¹,η¹manner. Solvent-vapour-assisted conversion between the polymorphic coordination polymers and solvent-vapour influence on the conversion of coordination polymers1to2aand2bis also explored. The transformations have been examined and confirmed by X-ray diffraction, NMR spectroscopy and thermal analyses, includingin situdiffraction studies of some transformations.