This paper describes the conversion of NiNd and NiTb compartment compounds into 1D coordination polymers or discrete tetranuclear 3d–4f compounds under microwave-heating conditions. Stirring a water–ethanol solution containing Ni(CH3COO)2·4H2O, o-vanillin, 1,3-diaminopropane and LiOH·H2O at 30°C produced [Ni(L1)2](H2O) (1), which possesses two imine–amine type ligands (HL1=((3-methoxysalicylidene)amino)-3-aminopropane). Compound 1 reacted with Nd(NO3)3·6H2O to give a dinuclear NiNd complex [NiNd(HL1)2(NO3)3](NO3)2 (2). When compound 2 was microwave-heated (700W) in water in the presence of a bispyridine (bipy=4,4′-bipyridine; bipp=1,3-bis(4-pyridyl)propane), a tetranuclear dimer bridged by two nitrato (NO3−) ligands was obtained: [NiNd(L2)(NO3)(μ3-NO3)(bipy)]2(OH)2(H2O)2(bipy) or [NiNd(L2)(NO3)(μ3-NO3)(bipp)]2(OH)2(H2O)4 (H2L2=1,3-bis((3-methoxysalicylidene)amino)propane). By contrast, compound 2 was converted into a 1D coordination polymer, [Ni2Nd2(L2)2(H2O)2(μ-NO3)3](OH−)3(H2O)6, when microwave-heated in the absence of the bispyridine. Compound 1 reacted with Tb(NO3)3·5H2O to give a dinuclear complex [NiTb(HL1)2(NO3)3]·(NO3)2, a NiTb analogue of compound 2. Microwave-heating this NiTb compound in water and in acetonitrile produced a 1D coordination polymer, [Ni2Tb2(L2)2(μ-NO3)3(H2O)2]·(OH−)3·4H2O, and a tetranuclear NiTb dimer, [NiTb(L2)(μ3-NO3)(NO3)(H2O)]2·(OH)2·(H2O)4, respectively. The NiTb compounds exhibited emission quenching of the Tb3+ ion, probably due to a Tb3+→Ni2+ energy transfer. In addition, the intensities of the emission spectra of these compounds did not increase when the lattice water molecules were removed.