Ellipsometric investigations of self-assembled monolayers (SAMs) of alkylsiloxanes on native silicon substrates and of organothiols on gold substrates were performed under in situ conditions with the substrate in direct contact with the adsorbate solution. Specially designed liquid cells matched for different incidence angles were used to carry out measurements in a range of organic solvents with different refractive indices as the ambient medium. The observed shifts in the ellipsometric phase angles a upon monolayer formation were found to depend very sensitively on the incidence angle and the refractive indices of the adsorbate him and the ambient solvent, from which a rather simple method for determining the refractive index of the adsorbate film, based on a variation of the ambient refractive index, was derived. Time-resolved in situ measurements of SAM formation in different solvents and onto different substrates yielded accurate kinetic information on the monolayer growth process and revealed hitherto unknown strong solvent effects on the growth rate.