Electronic spectra of Ni-SAPO-34 catalysts prepared by the rapid crystallization method, which show high performance in methanol conversion (i.e., ca. 90% ethylene selectivity with 100% conversion of methanol), suggest that the nickel ions are tetrahedrally coordinated with oxygen and are incorporated into the framework of SAPO-34. Nuclear magnetic resonance and electronic spectra as well as elemental analyses of samples quenched at various temperatures during temperature-programmed hydrothermal crystallization of the rapid crystallization method suggest that the aluminophosphate-like framework is developed first, the silicon atoms then being gradually incorporated into the framework, and the nickel ions falling into the tetrahedral sites at the last stage of crystallization.