We have synthesized layered surfactant-silicate mesophase composites using surfactant-templated synthetic routes under hydrothermal conditions. Local molecular ordering in both the bound surfactant and the inorganic framework for these mesophase composites has been observed and investigated using solid-state NMR and X-ray diffraction techniques. Synthesis parameters were systematically varied to determine the key factors that influence the molecular-ordering process. The dynamics and mobility of surfactant molecules at the interface have also been examined using NMR chemical-shift analyses, relaxation-time studies, and 2D WISE measurements. Results from this current work are compared with studies reported on other surfactant-silicate mesoporous materials.