Poly(ethylene oxide), (PEO), thin films of different thicknesses (220, 450, and 1500 nm) and molecular masses (4000, 8000, and 20000 g/mol) have been fabricated by spin-coating of methanol solutions onto glass substrates. All these samples have been recrystallized from the melt using a directional thermal gradient technique. Millimeter-size domains with crystallites uniformly, oriented in the direction of the thermal gradient are observed. Futhermore, the crystallites size and :orientation distribution are enhanced (e.g., increases and decreases, respectively) when film thickness is decreased, ultimately leading to a single-crystal-like behavior for 220 nm thick PEO films of mass 8000 g/mol. Interestingly, this fine microstructure is;partially retained after melting and subsequent-cooling back to ambient temperature for the highest molecular weight polymer allowing, in this particular case, to significantly decrease the distribution of crystal orientation obtained after crystallization using the thermal gradient technique.