Five polymorphous frameworks of cobalt(II) imidazolates (1–5) have been prepared by solvatothermal syntheses. Of these, compound 3 has already been synthesized in a gas-phase reaction by Seel et al. in 1969 and structurally characterized by Sturm et al. in 1975. The new synthetic strategy affords four polymorphous frameworks of cobalt(II) imidazolates (1, 2, 4, 5) of crystalline substances, of which the compound 4 (a = b = 23.450(3), c = 12.460(3) Å, tetragonal, I41cd, Z = 16) is an isomorphous compound of [Zn(im)2]∞, which was also synthesized in a gas-phase reaction in 1980. The frameworks of compounds 1 and 2 are porous and isostructural; they have the same framework topology that represents a novel uninodal (6,4)-net: 1: a = 18.513(4), b = 24.368(5), c = 9.2940(19) Å, orthorhombic, Fdd2, Z = 16; 2: a = 17.635(4), b = 27.706(6), c = 9.0810(18) Å, orthorhombic, Fdd2, Z = 16. The framework of compound 5 exhibits a topology of zeolitic structure with the unit-cell parameters: a = 24.3406(8), b = 9.4526(3), c = 24.8470(8) Å, β = 91.977(1)°, monoclinic, P21/n, Z = 4. All polymorphous frameworks of cobalt(II) imidazolates reflect the structural features of silica (SiO2) and also exhibit different magnetic behaviors, although the imidazolates transmit the antiferromagnetic coupling between the cobalt(II) ions in all cases. However, the uncompensated antiferromagnetic couplings arise from spin-canting are sensitive to the structures: compound 1 is an antiferromagnet with TN = 13.11 K; compounds 2–4 are weak ferromagnets (canted antiferromagnets): 2 shows a very weak ferromagnetism below 15 K, 3 exhibits a relatively strong ferromagnetism below 11.5 K and a coercive field (HC) of 1800 Oe at 1.8 K, and 4 displays the strongest ferromagnetism of the three cobalt imidazolates and demonstrates a TC of 15.5 K with a coercive field, HC, of 7300 Oe at 1.8 K. However, compound 5 seems to be a hidden canted antiferromagnet with a magnetic ordering temperature of 10.6 K.