Self-assembly of the partially fluorinated rigid molecules physisorbed at solution/graphite interface has been investigated by scanning tunneling microscopy. Upon adsorption, both the branched star-shaped compound 1 and the angulate rod 2 compromising diacetylene and acetylene interlinked benzene and pentafluorobezene formed two-dimensional chiral porous networks. The spontaneous formation of these architectures is likely attributed to the two effects: the compensation of the dipole moments of the branches and the formation of Ar-H...F hydrogen bonds. These results demonstrate that the immobilization of molecules at the liquid/solid interface can be driven by these weak