Two-dimensional (2D) self-assembly of two 1,3,2-dioxaborine derivatives was investigated by STM. The molecules consist of π system and steric end groups. A droplet of toluene solution containing the molecules was deposited onto HOPG for preparing the assemblies. STM images showed that the molecular structures affect the assembly structure. The dipole-dipole interaction and steric repulsion played important roles in the formation of the self-assembled monolayers.