Polymer blends of poly(propylene) (PP) and polyacetal (polyoxymethylene, POM) with ethylene vinyl alcohol (EVOH) copolymers were investigated by differential scanning calorimetry (DSC), rheological, tensile, and impact measurements, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The PP-POM-EVOH blends were extruded with a co-rotating twin-screw extruder. The ethylene group in the EVOH is partially miscible with PP, whereas the hydroxyl group in the EVOH can form hydrogen bonding with POM. The EVOH tends to reside along the interface, acting as a surfactant to reduce the interfacial tension and to increase the interfacial adhesion between the blends. Results from SEM and mechanical tests indicate that a small quantity of the EVOH copolymer or a smaller vinyl alcohol content in the EVOH copolymer results in a better compatibilized blend in terms of finer phase domains and better mechanical properties.