Promoter (phosphate)-enhanced crystallization of MCM-41 has been studied by multinuclear solid-state NMR spectroscopy with use of C-13, Si-29, and P-31 as probe nuclei. The structure building Q(4) units, in addition to the silanol nests built by the Q(2) and Q(3), are identified and quantified through Si-29 MAS NMR. A measure of the relative amount of the silanol nests, present over the T-sites formed, was determined from the ratio (Q(2) + Q(3))/Q(4) and is found to be smaller in the mesoporous material prepared by the phosphate promoter assisted synthesis. Signal evolution for the Q(3) and Q(4) resonances in H-1-Si-29 CP dynamics experiments shows that cross-polarization buildup rates (T-IS(-1)) are unchanged for the end material prepared with phosphate promoter. C-13 signal evolution in H-1-C-13 CP dynamics experiments for the surfactant cetyl trimethylammonium bromide (CTABr), used as a template, is markedly different when it is confined within the mesopores of MCM-41. An enhanced mobility for the surfactant molecule is inferred and is consistent with the liquid crystal templating mechanism proposed earlier for the formation of mesoporous MCM-41 materials. Further, IT MAS experiments show that there is no incorporation of the phosphate promoter within MCM-41 during the hydrothermal synthesis.