Linear polymers with monodendron side groups adsorb on highly oriented pyrolytic graphite (HOPG) in a remarkably regular pattern. The wormlike molecules have been depicted individually by scanning force microscopy with their long axis aligned according to the S-fold symmetry of HOPG. The positional and orientational order of the adsorbed molecules is explained by the specific interaction of the alkyl substituents of the monodendrons with the HOPG surface. Direct evidence of the epitaxial adsorption was found by scanning tunneling microscopy of monolayers of the monomeric dendrons on HOPG. Ordering depended on the number of the alkoxy substitutes on the monodendrons. If the substitution of the monodendrons by the alkoxy groups was too dense, regular adsorption of the alkyl tails was impeded.