Using the polymer blending method, conductive materials and waterborne polyurethane (WPU) were mixed to fabricate conductive composite films for application in electromagnetic shielding. First, nitric acid was used to purify the multi-walled carbon nanotubes (MWCNT). Second, sodium dodecyl sulfate (SDS) was utilized to disperse the carbon nanotubes, and then they were mixed with 8 microm diameter and 2 mm long stainless steel fibers (SSF) in the WPU by the polymer blending method. Finally, the thickness of 0.25 mm of conductive composite film was fabricated by means of coating. According to the ASTM D4935-99 standard, a coaxial transmission line was used to measure the electromagnetic shielding effectiveness (EMSE) of conductive composite film within the range of 50 MHz approximately 3.0 GHz. Moreover, the influence of the prior and posterior dispersion of carbon nanotubes dispersed on electromagnetic shielding was dealt with in the paper. Results demonstrated that the conductive composite film, within 50 MHz approximately 3.0 GHz, fabricated by the 15 wt% of the multi-walled carbon nanotubes and 30 wt% of the stainless steel fibers can achieve the maximum of the electromagnetic shielding effectiveness, 34.86 dB, and its shielding effect, 99.9%.