This work targeted the synthesis of 4-coordinated aluminosilicate sites of general formulas [L-AlO3] and [AlO4] -, embedded in loose silicate matrices by utilizing the first step of a previously published two-step non-hydrolytic sol-gel procedure. The synthetic procedure proved to be flexible enough to accommodate a multitude of ligands, reactive groups, and solvents while it showed convergent behavior, leading only to several types of sites with well-defined Al NMR signatures. Al TQ/MAS NMR spectroscopy allowed for the observation and confident assignment of Lewis acid sites of general formulas L-Al(OCUBE)3 (L = THF, py, Et3N, TEPO) and L-Al(O2CUBE)(OCUBE) (L = THF, py). While the products always contained the targeted Lewis acid species, only TEPO-Al(OCUBE) 3 could be obtained as a true single-site material.