Oligo(p-phenylenevinylene) (OPV) dimers, tetramers and hexamers, were organized in highly organized 2D crystals on graphite by spontaneous self-assembly. The unit cell parameters of these monolayers could be detd. and a profound effect of the length of the p-conjugated backbone on the adlayer structure was discovered. For all oligomers, the OPV-units were aligned in rows, with the alkyl chains residing in between the rows. Only trans-vinylene bonds were obsd. In the hexamer, the organization was strongly detd. by the p-system. Shortening the p-conjugated moiety led to monolayer structures controlled by the alkyl side chains. The chiral oligomers (hexamer and tetramer) formed chiral monolayers. In the case of the tetramer, the p-conjugated backbone was oriented clockwise with respect to the normal of the rows while in the case of the hexamer this orientation was counterclockwise.