A series of phenol-formaldehyde-polyethylene glycol polyether polyols (PF-PEGs) were synthesized through the condensation polymerization and etherification of phenol, formaldehyde, and poly(ethylene glycol) (PEG) under alkaline conditions and subsequently reacted with 1,6-hexamethylene diisocyanate to obtain polyurethane (PU) films using acetone as solvents. The influence of phenol and formaldehyde to PEG mass ratio ((P + F)/PEG) on the hydroxyl number of PF-PEGs and mechanical properties, thermal stabilities, crystallization behaviors, as well as microstructure of polyurethane composite films were studied using chemical analysis, mechanical tests, thermogravimetric analyses (TGA), dynamic mechanical analyses (DMA), X-ray diffraction (XRD), scanning and transmission electron microscopies (SEM and TEM), respectively. Results demonstrated that PF-PEGs with (P + F)/PEG of 50/50 had the highest hydroxyl number of 323 mg K(OH)/g. The incorporation of phenol and formaldehyde into PEG improved the mechanical properties of polyurethane films, glass transition temperature (Tg), and thermal properties but resulted in the brittleness characteristic of the composite films and low crystallization properties. Moreover, the synthesis mechanism of PF-PEGs polyurethane composite films was revealed, which would provide a theoretical base for the preparation of the rigid polyurethane foams based on phenolic resins.