Complex molecular layering of OH-terminated perfluoropolyalkylether films over amorphous carbon surfaces has been observed using spatially resolved microellipsometry. The first layer is diffusive in nature, and the subsequent layers exhibit sharp steps of about twice the thickness of the first layer. This behavior, characteristic of a coexisting two-dimensional gas, with cohesive, liquidlike multilayers, is in clear contrast with that of the ${\mathrm{CF}}_{3}$-terminated analog, which shows a smooth diffusive profile. In this particular case, spreading, for thickness greater than one monolayer, can be exactly described by a Poiseuille flow in a disjoining pressure gradient originating solely from van der Waals interactions. For both types of polymers, diffusion rate reaches a maximum at full monolayer coverage, and decreases in the submonolayer regime. Spreading for both types of polymers unambiguously follows a ${t}^{1/2}$ time dependence.