A new series of coordination-network compounds containing Ni(CN)(2) and MX (M = Rb, Cs; X = Cl, Br) quasi two-dimensional sheets has been synthesized and structurally characterized. The tetragonal crystal structure (/4/mmm, no. 139) can be derived from the distorted perovskite type. Chemically, the Lewis-acidic Ni(CN)(2) moieties accept halide ligands, resulting both in slightly elongated [Ni(NC)(4)X-2](4-) octahedra and strongly elongated [Ni(CN)(4)X-2](4-) octahedra that are charge-balanced by M+ cations. Quantum-chemical calculations of the effective Hamiltonian crystal field (EHCF) type indicate the simultaneous presence of high- and low-spin Ni2+ in a 1:1 ratio, in agreement with GGA+U and UV studies reported here. Our magnetic susceptibility data also corroborate the theoretical findings. An analysis of the magnetic superexchange paths in the new series of compounds is performed as well as that of the tentative magnetic state of the series.