As an alternative method for processing polyaniline (PANI) from its conducting (protonated) state, vacuum casting of PANI from a methanesulfonic acid (MSA) solution provided films with electrical conductivity values of about 130-150 S/cm. In addition, we similarly prepared blended films of PANI.MSA and poly(p-phenylene benzobisthiazole) (PBZT). This process eliminated the need for a subsequent protonation step and had the additional advantage that the conjugated PBZT may provide alternative conducting pathways. Conductivity values of the composite films ranged from 100 pS/cm to 124 S/cm, and the films displayed critical concentration behavior with a PANI threshold concentration of 2.75% and a critical exponent of 4. Transmission electron micrographs displayed phase-separated regions with PANI forming a continuous network at high concentrations. Thermogravimetric analysis results demonstrated the thermal and thermooxidative stability advantage of the blends due to the PBZT component.