Cellulose acetate (CA)/polyethylene glycol (PEG)/triacetin (TA) blend films with different composition ratios were prepared by solution casting method to evaluate the effect of TA on the secondary structure and mechanical properties CA/PEG blend films. The cast CA/PEG blend films were drawn under various zone-drawing conditions determined by rheometry. Maximum draw ratio, degree of orientation, crystallinity, surface morphology, and mechanical properties were studied at different TA concentrations. CA/PEG/TA films had higher drawability and degree of orientation than CA/PEG and CA/TA films. Also, the mechanical properties of CA/PEG/TA films were better owing to their ordered structure. TA acted as a compatibilizer to facilitate the extension of polymers in the direction of zone-drawing, when CA or CA/PEG blend films were drawn. This could be a potential solution to the problem of low tensile strength in melt-spun CA/PEG fibers.