The formation of a silicoaluminophosphate-based molecular sieve SAPO-44 has been investigated in the present study. Particular attention was directed toward the characterization of the intermediate phases formed at different stages during the synthesis. The changes in the long-range ordering of the gel phases as a function of crystallization time was monitored by powder X-ray diffraction, and the development of the local structure of P, Al, and Si atoms was followed by P-31, Al-27, and Si-29 magic-angle spinning NMR. H-1 --> P-31 cross polarization (CP) was employed to differentiate the P sites in, different phases coexisting in the sample. Several Al-27/P-31 and Al-27/Si-29 double-resonance NMR experiments such as CP and transferred echo double-resonance were also utilized to identify the nature of the intermediate phases, and to select the P-O-Al and Si-O-Al bonding connectivities. FT-Raman spectroscopy was used to gain the information regarding the evolution of the porosity in the framework and the immediate environments around the template molecules. On the basis of the experimental results, a possible route for the formation of SAPO-44 is discussed.