We have used controlled crystallization of elementally modulated reactants to prepare a series of kinetically stable, crystalline skutterudites (M'xM4Sb12 where M' = vacancy, RE, Hf,…; M = Ni, Fe, Co) and crystalline superlattices composed of promising thermoelectric materials. For the bulk synthesis of skutterudites, low angle diffraction data demonstrates that the elemental layers interdiffuse at temperatures below 150°C. Nucleation of the skutterudite structure occurs with at large exotherm on annealing at temperatures below 200°C regardless of the ternary metal. All of the metastable ternary compounds and the new metastable binary compounds were found to decompose exothermically on higher temperature annealing. The decomposition temperature ranged from 250°C for the binary compound NiSb3 to above 550°C for the rare earth containing cobalt compounds. The occupation of the ternary site was found to depend on the composition of the initial reactant and was varied from 0 to 1. Full occupancy typically required an excess of the filling cation. The lattice parameters of the compounds prepared at low temperatures are distinctly smaller than those prepared using traditional synthetic approaches. High temperature annealing converts the lattice parameters of the low temperature compounds to those prepared at higher temperatures using traditional synthetic approaches. Diffraction patterns of crystalline superlattices containing skutterudites prepared using elementally modulated reactants show splitting of high angle diffraction maxima as well as the presence of the expected low angle diffraction pattern from a supperlattice. The skutterudite superlattices are stable with respect to low temperature annealing.