Indium-tin-oxide (ITO) electrode surfaces were modified using thin polymeric films of ethoxylated polyethylenimine (PEIE) and poly(3,3′-([(9′,9′-dioctyl-9H,9′H-[2,2′-bifluorene]-9,9-diyl)bis(4,1-phenylene)]bis(oxy))bis(N,N-dimethylpropan-1-amine)) (PFPA-1) to investigate the resultant work function and its stability in ambient atmosphere. Both PEIE and PFPA-1 were found to significantly reduce the ITO work function, as a result of a surface dipole at the ITO-polymer interface. After aging for two weeks in ambient air atmosphere, the N-side groups and OH groups in PEIE-modified ITO were found to realign themselves away from the polymer surface, resulting in an orientation more parallel to the surface normal and thus in an increase in work function from 3.5 to 3.8eV. The work function of PFPA-1-modified ITO was found to increase from 3.65 to 4.1eV after two weeks of aging in air due to a complete re-orientation of the polar side chains away from the surface, aligning the dipoles more parallel to the surface normal. In both PEIE and PFPA-1 samples, the hydrophobic aliphatic carbon was found to dominate the polymer surface, after aging.