Brewster-angle reflection ellipsometry and surface optical second harmonic generation were used to study the growth of 4'-n-octyl-4-cyanobiphenyl (8CB) films evaporated in air onto polymeric and quartz glass substrates. The layer-by-layer growth of the films terminates after formation of two distinctive interfacial layers. Both of these two layers are polar and tilted. In the first layer the molecules lie nearly flat on the surface, while in the second layer they point on average about 50 degrees toward the surface normal. The dipole moment of the second layer has a lower magnitude and an opposite direction with respect to the dipole moment of the first layer.