Conducting films of dodecylbenzenesulfonic (DBSA)-doped polyaniline/polyimide (PANI/PI) blends with various compositions were prepared by solvent casting followed by a thermal imidization process. Electrical and physical properties of the blends were characterized by infrared spectroscopy, an X-ray diffraction technique, thermal analysis, a UV-vis spectrophotometer, a dielectrometer, and conductivity measurements. The blends exhibited a relatively low percolation threshold of electrical conductivity at 5 wt % PANI content and showed higher conductivity than that of pure DBSA-doped PANI when the PANI content exceeded 20 wt %. A lower percolation threshold and a lower compatibility was shown between the two components in the blends than those of PANI-camphorsulfonic acid/polyamic acid (PANI-CSA/PAA). A well-defined layered structure due to the alignment of the long alkyl chain dopant perpendicular to the PANI main chain was evidenced by WAXD spectra.