Nanostructured polyanilines (PANIs) are selected quite often as the matrix for the synthesis of inorganic/conductive polymer composites due to their excellent optical, electrical and magnetic properties. Herein both 2D lamellar PANI and the corresponding composite loading TiO2 species were successfully prepared from a microemulsion system, as composed by dodecyl benzenesulfonic acid (DBSA) and water. The composite was achieved through a simultaneous polymerization of aniline in the presence of ammonium persulfate and hydrolysis of tetrabutyl titanate. Scanning electron microscopy (SEM) images indicate clearly that 2D PANI lamella are formed through organization of small PANI sheets. The inter-lamellar distance of PANI and that of TiO2/polyaniline composite, as derived from X-ray diffraction (XRD), is about 3.4 nm (nearly twice the length of one DBS molecule), suggesting that PANI and double-layered DBSA species are arranged in an alternated way. FTIR spectrum displays that PANI chains exhibit quinonoid and benzenoid strutures while both Raman and X-ray photoelectron spectroscopy (XPS) indicate that rutile TiO2 is produced upon hydrolyzation of tetrabutyl titanate in the microemulsion system. Moreover, UV-Vis spectrum suggests that the electronic absorption behaviour of PANI species is influenced upon loading TiO2.