Methanol adsorbed on the (100) face of MgO has been studied at room temperature and elevated methanol pressures using transmission Fourier transform infrared spectroscopy. From these investigations, we find evidence of two structures for the adsorbed methanol. At low coverages, the methanol molecules congregate into two-dimensional islands that are strongly associated with the substrate. The properties of this submonolayer-to-monolayer thin film are similar to those of solid methanol. Once the available surface sites are occupied and a complete monolayer has formed, the methanol begins to condense in multilayers, creating a thin film on the surface with properties similar to liquid methanol.