Novel pharmacologically active silicon—titanium—zinc- and silicon—titanium—boroncontaining glycerohydrogels were synthesized by the sol—gel method using silicon, titanium, zinc, and boron glycerolates as biocompatible precursors. The compositions and structural features of the hydrogels were studied by transmission electron microscopy, scanning electron microscopy, IR spectroscopy, atomic emission spectrometry, and elemental analysis methods. The disperse phase and liquid water—glycerol medium of the hydrogels were isolated by cold exhaustive extraction with ethanol and characterized. The 3D polymeric network of the gels is formed by the products of hydrolysis and subsequent (co)condensation of silicon-/silicon— boron-containing precursors. Titanium and zinc glycerolates undergo no hydrolytic transformations under gelation conditions and exist in the cells of the 3D polymeric network in the form of amorphous nanoparticles that are not linked to the network by covalent bonds. Models of the structures were proposed. The gels are characterized by antimicrobial activity, which is more pronounced for the silicon—titanium—boron-containing gel, and they can be considered as promising drugs for topical treatment prepared by the simple, environmentally friendly, and cost-eff ective method.