The effects of fabrication process and solvent on the structure of polyaniline (PANI) emeraldine base films and their intrinsic properties are examined. Freestanding films of PANI base fabricated from N,N'-dimethyl propylene urea (DMPU) and N-methyl-2-pyrrolidone (NMP) solutions, by casting and spin-coating procedures and subsequently drawn to different draw ratios, are examined. X-ray diffraction studies show that the PANI films processed from DMPU solution have a noncrystalline structure, whereas the PANI films cast from NMP solution are partially crystalline. The crystal structure is in conformity with the orthorhombic unit cell (EB-II) reported earlier. However, the c parameter of the unit cell was found to be slightly lower than the literature values. A near-infrared waveguide technique was used to determine the three-dimensional refractive indices of the processed and drawn PANI films. The anisotropies developed by the different fabrication and deformation procedures were compared and found to differ. Coupling birefringence and quantitative infrared dichroism measurements yields the intrinsic birefringence and transition moment angles of the infrared absorption bands of PANI.