We have studied liquid crystal (LC) molecular alignment on rubbed and photoaligned surfaces. Particular attention was paid to the intermolecular liquid crystalline interaction. We will first show that uniform molecular orientation on a rubbed surface does not mean spatially uniform interaction between the surface and LC molecules. Rather LCs tend to align themselves through LC interaction. The existence of nonuniformity of rubbing was successfully visualized by double surface treatment. The importance of intermolecular LC interaction was also found in the orientation formation process in 5CB evaporated on rubbed and photoaligned surfaces. By simultaneously analyzing polarized UVNIS absorption and second-harmonic generation (SHG) using the maximum entropy method, we succeeded in obtaining the temporal variation of the orientational distribution functions in the film forming process. The distribution anisotropy and pretilt are found to be generated under the influence of intermolecular LC interaction.