Poly(vinylidene fluoride-co-hexafluoropropylene)/polyaniline (PVDF-co-HFP/ PAni) conductive blends were prepared by two methodologies involving the in situ polymerization in two different media and dry blending approach using ball milling. Dodecylbenzenesulfonic acid (DBSA) was used both as surfactant and as protonating agent in PAni synthesis. X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-visible (UV-Vis) spectroscopy, and thermogravimetric analysis were used for characterizing the blends. PAni and PVDF/PAni prepared by in situ polymerization in H 2 O/toluene medium exhibited superior electrical conductivity, higher thermal stability and significantly higher electromagnetic interference shielding effectiveness (EMI SE) than those prepared in H 2 O/dimethylformamide (DMF) medium. PVDF/PAni with high-PAni content (>40%) prepared by the dry blend approach presented higher conductivity and EMI SE than those prepared by in situ polymerization.