Luminescence and energy transfer in [Zn_1-xRu_x(bpy)₃][NaAl_1-yCr_y(ox)₃] (x ≈ 0.01, y = 0.006 − 0.22; bpy = 2,2‘-bipyridine, ox = C₂O₄^2-) and [Zn_1-x-yRu_xOs_y(bpy)₃][NaAl(ox)₃] (x ≈ 0.01, y = 0.012) are presented and discussed. Surprisingly, the luminescence of the isolated luminophores [Ru(bpy)₃]²⁺ and [Os(bpy)₃]²⁺ in [Zn(bpy)₃][NaAl(ox)₃] is hardly quenched at room temperature. Steady-state luminescence spectra and decay curves show that energy transfer occurs between [Ru(bpy)₃]²⁺ and [Cr(ox)₃]^3- and between [Ru(bpy)₃]²⁺ and [Os(bpy)₃]²⁺ in [Zn_1-xRu_x(bpy)₃][NaAl_1-yCr_y(ox)₃] and [Zn_1-x-yRu_xOs_y(bpy)₃] [NaAl(ox)₃], respectively. For a quantitative investigation of the energy transfer, a shell type model is developed, using a Monte Carlo procedure and the structural parameters of the systems. A good description of the experimental data is obtained assuming electric dipole−electric dipole interaction between donors and acceptors, with a critical distance R_c for [Ru(bpy)₃]²⁺ to [Cr(ox)₃]^3- energy transfer of 15 Å and for [Ru(bpy)₃]²⁺ to [Os(bpy)₃]²⁺ energy transfer of 33 Å. These values are in good agreement with those derived using the Förster−Dexter theory.