Polyimide films treated with an alkali and ion exchange undergo surface-confined hydrolysis to produce polyimide composites. On the other hand, it is unclear what impact this method has on the mechanical properties of PI films. This paper reports the effects of the mechanical properties of PI films exposed to an alkali (KOH) solution with different treatment time. The mechanical properties of the re-cycloimidization PI films were improved when the proper initial KOH treatment time was used. The reason might be that PI could effectively reduce the formation of the shear zone to cracks due to the increase in ductility after the proper KOH treatment and more ductile PI chains led to re-orientation at the drawing process. Therefore, the strength and elongation of the re-cycloimidization PI films were better than those of the pristine PI films. This study focused on the effects of the KOH treatment on the mechanical properties of the PI film for the first time and proposed a mechanism to explain the reason that the appropriate time of KOH treatment can enhance the mechanical properties. The results presented here can provide guidelines for preparing composite PI films via ion-exchange by the proper KOH treatment time in future studies.