The atomic force microscope (AFM) has been used to characterize both microscopic and macroscopic structure in solution-cast films of high-density polyethylene (HDPE) on mica. Upon sample quench both large-scale spherulitic morphologies and smaller scale individual polyethylene lamella were easily distinguished and amorphous and crystalline regions inferred. Small angle light scattering (SALS) was used to confirm spherulitic structure and verify quantitative AFM size measurements. Upon anneal, spherulitic structure vanishes as revealed by both AFM and SALS and as predicted in previous studies of polyethylene. This study verifies the ability of the AFM to characterize polymeric films without physical alteration over a large range of length scales.