We have used several solid-state NMR techniques in conjunction with powder X-ray diffraction (XRD) and FT-Raman spectroscopy to characterize the structures of the intermediate phases of AlPO4-11 molecular sieve synthesis. The evolution of the gel phases as a function of crystallization time was followed by P-31 and Al-27 magic angle spinning (MAS) NMR to obtain information on the local environments of Al and P atoms and by powder XRD to detect the long range ordering of the gel samples. We have utilized Al-27 triple-quantum MAS (3QMAS) to gain additional resolution for monitoring the incorporation of different Al sites into the framework during the crystallization. Al-27/P-31 double resonance techniques such as cross polarization (Cl?), transfer of populations by double-resonance, and rotational echo double-resonance have been utilized to select the P-31-O-Al-27 bonding connectivities within the gel phases. The H-1-->P-31 CP enables differentiation of the phosphorus sites in different phases coexisting in the same solid sample. FT-Raman spectroscopy also provides insight into the interactions between organic template and inorganic gel species as well as the evaluation of the pore system. The present work clearly demonstrates that the dipolar-coupling based double-resonance techniques can provide important connectivity information regarding the structures of the gels, which are not readily available from simple MAS experiments.