Sol-gel synthesis of filled polyaluminosilicates with macromolecules having a dendrimer morphology (M calc ≈ 480 000) was developed. The software package Gaussian B3LYP/6-31G(d) was used to assess the possible mechanism by which nuclei of dendrimer molecules are created, with the subsequent generation of crowns of branched ensembles capable of accommodating up to 70 wt % nano-Al2O3 as a filler. The data furnished by transmission electron microscopy of the samples are in agreement with the suggested mechanism of generation and growth of dendrimers. The main results were obtained on filled aluminosilicate samples that contain 70 wt % nano-Al2O3 and exhibit a high wear resistance in tribological tests.