Dimethyl carbonate (DMC) is a versatile and green reagent, used as a precursor for resins and fuel additives and also as a methylating and carbonylating agent. DMC has been generally synthesized using the toxic and hazardous phosgene (ClCOCl) as a reagent. Mg–Al hydrotalcite-like nanolayers on silica lyogels were prepared, activated by calcination, and tested as catalysts in the direct carboxylation reaction of methanol. The nanolayers supported on silica lyogels showed an important improvement (from 4.2 to 15.9%) and high stability in the direct synthesis reaction of DMC from CO2 and methanol. In this context, LG-HTO is a further advance in the design of more-efficient heterogeneous catalysts and reaction systems for valorising CO2 as a potential source of economic and environmental benefits for the industry and society.