Mesoporous dual layers of polyaniline (PANI) supported selenium-tellurium (Se0.5Te0.5) films have been synthesized from lyotropic liquid crystalline (LLC) template with Brij56 surfactant. The optical texture of LLC is observed by polarized optical microscopy (POM). The structure of the dual-layer film is characterized by low-angle and wide-angle X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The band gap of Se0.5Te0.5/PANI dual-layer films was estimated to be 0.9 eV, and the band gap of Se0.5Te0.5 films was calculated to be 1.4 eV, indicating that the incorporation of PANI into Se0.5Te0.5 enhances its electron transfer.