The work function of the indium tin oxide electrode (ITO) modified by a self-assembled monolayer (SAM), which is used as an electrode in organic electroluminescent (EL) devices, was investigated in this study. It is revealed that chemical modification of ITO with p-substituted with different terminal groups (NH2-, Cl-, and CF3-) benzoic acids as a SAMs material with carboxyl binding group is caused to increase the work function of the ITO electrode. Through a self-assembly process, the transmittance of the ITO with a SAM was not changed. The work function change of ITO with various SAM was measured by using cyclic voltammetry. Characteristics of EL devices were increased because the energy barrier was decreased in an interface between the ITO and an organic layer in the EL devices. The correlation of the work function change and the performance of the chemically modified EL devices was estimated.