The structural ordering of mesogenic-terminated carbosilane dendrimers within surface monolayers was studied. We have shown that despite their symmetrical spherical shape layering with average spacing close to 6 nm is observed for dendrimers with butoxyphenylbenzoate terminal groups deposited on hydrophilic silicon substrates. The molecular layered packing is formed by flattened dendritic molecules with terminal groups stacking into bilayers. This layered ordering is controlled by strong interactions between the polar mesogenic groups and the hydrophilic surface and by microphase separation of the dendritic core and terminal groups. The dilution of the outer mesogenic shell with a nonmesogenic component partially disturbs the layered packing within the monolayer. Complete disruption of the regular lamellar ordering is observed if butoxypherylbenzoate terminal groups are replaced with shorter and more polar cyanbiphenyl groups. For all dendrimers studied here the replacement of the hydrophilic support with hydrophobic one prevents the formation of dense surface layers due to antagonistic interactions between polar terminal groups and a methyl-terminated surface. However, the presence of the nonmesogenic hydrophobic terminal groups stimulates the formation of two-dimensional circular molecular structures which are characteristic of columnar LC dendrimer phases.