In analogy to the [M^II(bpy)₃]²⁺ cations, where M^II is a divalent transition-metal and bpy is 2,2‘-bipyridine, the tris-chelated [M^III(bpy)₃]³⁺ cations, where M^III is Cr^III or Co^III, induce the crystallization of chiral, anionic three-dimensional (3D) coordination polymers of oxalate-bridged (μ-ox) metal complexes with stoichiometries [M^II₂(ox)₃]_n^2n- or [M^IM^III(ox)₃]_n^2n-. The tripositive charge is partially compensated by inclusion of additional complex anions like ClO₄^-, BF₄^-, or PF₆^- which are encapsulated in cubic shaped cavities formed by the bipyridine ligands of the cations. Thus, an elaborate structure of cationic and anionic species within a polymeric anionic network is realized. The compounds isolated and structurally characterized include [Cr^III(bpy)₃][ClO₄] [NaCr^III(ox)₃] (1), [Cr^III(bpy)₃][ClO₄][Mn^II₂(ox)₃] (2), [Cr^III(bpy)₃][BF₄] [Mn^II₂(ox)₃] (3), [Co^III(bpy)₃][PF₆][NaCr^III(ox)₃] (4). Crystal data:  1, cubic, P2₁3, a = 15.523(4) Å, Z = 4; 2, cubic, P4₁32, a = 15.564(3) Å, Z = 4; 3, cubic, P4₁32, a = 15.553(3) Å, Z = 4; 4, cubic, P2₁3, a= 15.515(3) Å, Z = 4. Furthermore, it seemed likely that 1,2-dithiooxalate (dto) could act as an alternative to the oxalate bridging ligand, and as a result the compound [Ni^II(phen)₃][NaCo^III(dto)₃]·C₃H₆O (5) has successfully been isolated and structurally characterized. Crystal data:  5, orthorhombic, P2₁2₁2₁, a = 16.238(4) Å, b = 16.225(4) Å, c = 18.371(5) Å, Z = 4. In addition, the photophysical properties of compound 1 have been investigated in detail. In single crystal absorption spectra of [Cr^III(bpy)₃][ClO₄][NaCr^III(ox)₃] (1), the spin−flip transitions of both the [Cr(bpy)₃]³⁺ and the [Cr(ox)₃]^3- chromophores are observed and can be clearly distinguished. Irradiating into the spin-allowed ⁴A₂ → ⁴T₂absorption band of [Cr(ox)₃]^3- results in intense luminescence from the ²E state of [Cr(bpy)₃]³⁺as a result of rapid energy transfer processes.