Electronic structures at the Si/SiO2/molecule interfaces were studied by Kelvin probe techniques (contact potential difference) and compared to theoretical values derived by the Helmholtz equation. Two parameters influencing the electronic properties of n-type < 100 > Si/SiO2 substrates were systematically tuned: the molecular dipole of coupling agent molecules comprising the layer and the surface coverage of the chromophoric layer. The first parameter was checked using direct covalent grafting of a series of trichlorosilane-containing coupling agent molecules with various end groups causing a different dipole with the same surface number density. It was found that the change in band bending (Delta BB) clearly indicated a major effect of passivation due to two-dimensional polysiloxane network formation, with minor differences resulting from the differences in the end groups' capacity to act as "electron traps". The change in electron affinity (AEA) parameter increased upon increasing the dipole of the end group comprising the monolayer, resulting in a range of 600 mV. Moreover, a shielding effect of the aromatic spacer compared with the aliphatic spacer was found and estimated to be about 200 mV. The density effect was examined using the 4-[4-(N,N-dimethylamino phenyl)azo]pyridinium halide chromophore which has a calculated dipole of more than 10 D. It was clearly shown that upon increasing surface chromophoric coverage an increase in the electronic effects on the Si substrate was observed. However, a major consequence of depolarization was also detected while comparing the experimental and calculated values.