A facile method was developed to synthesize porous polyimide (PI) films with enhanced adhesion to Cu foil. Various amounts (0.1–4 wt %) of polystyrene (PS) spheres with the diameter of 250 nm were mixed with the PI precursor synthesized from pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline in N,N′-dimethylacetamide. PS was decomposed during thermal imidization process to create the porous PI structure. The increase in surface area and surface roughness was observed from the obtained porous PI films and was a function of the PS content up to 4 wt %. A significant improvement in the adhesion strength between porous PI film and Cu foil, which was determined by 90° peel test, was achieved. The adhesion strength of PI containing 4 wt % PS to Cu was 1.53 kgf/cm compared with pure PI of 1.08 kgf/cm. Meanwhile, the synthesized porous PI films exhibit sufficient mechanical strength and thermal stability for practical applications.