A series of star-shaped oligofluorenes end-capped with carboxylic acid groups were synthesized. Different numbers of carboxyl groups that can form hydrogen bonds, and long alkane chains that have stabilizing effects, were intentionally introduced. The resulting molecular architectures of the so-prepared star-shaped oligofluorenes at the liquid-solid interface were investigated by scanning tunneling microscopy. It is found that the number of hydrogen-bonding groups and the symmetry of the target molecules have crucial influences on the structures of the ordered assemblies.