A new non-interpenetrated two-dimensional (2D) rectangular-grid coordination polymer, {[Co(L)(2)(H2O)(2)]center dot(BF4)(2)center dot 4DMF}(n) (1), has been synthesized using a new rod-like ligand, 3,5-bis(4-imidazol-1-ylphenyl)-[1,2,4]triazol-4-ylamine (L). Weakly H-bonded BF4- anions present within the voids can be exchanged by CIO4-and NO3- anions to generate {[Co(L)(2)(H2O)(2)]center dot(CIO4)(2)center dot 2DMF center dot 2H(2)O}(n) (2) and {[Co(L)(2)(H2O)(2)]center dot(NO3)(2)center dot 2DMF center dot 2H(2)O}(n) (3) in single-crystal-to-single-crystal (SC-SC) manner. In the case of exchange by Cl ion, the crystallinity is not maintained, and so it is proven by IR spectroscopy, PXRD, and elemental analysis. In addition, 3 shows an interesting structural transformation (2D -> 1D) with bond rupture/formation leading to the formation of a new coordination polymer, {[Co(L)(2)(H2O)(2)]center dot(NO3)(2)center dot 2DMF center dot H2O}(n), (5), again in SC-SC fashion.