Porous coordination polymers (PCPs) have received considerable attention because of their diverse topologies and potential applications in storage, separation, and catalysis. [1][2][3][4][5][6] Besides porosity, stability, and pore shape and size, framework flexibility and pore-surface modifications are currently considered to be the key factors for the next generation of PCPs. [2, 3] The guest-responsive pores of flexible PCPs provide strong confinement effects for specific guest molecules by shrinking or expanding in different guest-inclusion states, which may also be directly visualized by crystallographic analysis if the host framework is strong enough to undergo transformation from single crystal to single crystal (SCSC). [4, 5] The incorporation of coordinatively unsaturated metal centers (UMCs) [3d] into a porous host is very attractive as UMCs can strongly interact with guest molecules. Compared to inorganic zeolites, polymeric matrices, and clays, UMCs located inside PCPs have uniform arrangements and wellunderstood surrounding environments. However, successful immobilization of UMCs onto the PCP pore surface is still rare as only a few PCPs are stable upon thermal liberation of volatile coordinated ligands. [6] Low-coordinate silver(I) is a potential UMC because silver(I) centers can adopt diverse coordination environments. Silver(I)-exchanged zeolites were used in alkanealkene separation studies as the silver(I) center has a high affinity for unsaturated hydrocarbon molecules which arises from Agβ’β’β’p interactions. [7] However, it is very difficult to restrict the coordination number of Ag I by using common pyridine-or carboxylate-like ligands. Conversely, the metal coordination number is always equal to, or lower than, the number of nitrogen atoms in binary metal azolates, such as pyrazolates, imidazolates, and triazolates. [8] A 3D cationic silver-triazolate framework composed of linear coordinate Ag I centers was shown to undergo drastic, temperature/guest-Scheme 1. Use of Me 4 bpz 2Γ ligands and Ag + ions to construct a flexible framework with two-coordinate Ag centers.