Herein we present synthesis, characterization, and catalytic application of highly homogeneous amorphous aluminosilicates with medium strength acid sites. These catalysts were prepared by non-hydrolytic sol-gel (NHSG), an unconventional synthetic method. The dispersion of aluminum is very homogeneous (XPS, ToF-SIMS) within the mesoporous silicate matrix (N2 physisorption). Catalysts are amorphous and possess high amount of medium strength acid sites (NH3-TPD). Decisively, this NHSG preparation technique also allows for the direct and homogeneous incorporation of organic groups using organosilane precursors. Both aliphatic and aromatic as well as terminal and bridging groups were used (IR and SS NMR spectroscopy) with the intention to increase the hydrophobicity of the surface (H2O physisorption) and thereby boosting the performance and stability of the catalysts during the dehydration reaction.