PANI/TiO2 nano-composites with different amount of nanometer TiO2 were synthesized by using reverse micelle formed from cationic surfactant cetyltrimethyl ammonium bromide (CTAB) as the template. The structure and properties of PANI/TiO2 nano-composites were investigated by FTIR, UV-Vis, TG, TEM and photoluminescence spectroscopy. The self-assembly mechanism of PANI/TiO2 nanorods composites in reversed micelle was discussed briefly. The results indicate that the synthesized nano-composites are PANI/TiO2 nanorods with an average diameter and length around 30-40 nm and 400 nm respectively. The infrared spectrum shows that a strong interaction exists between PANI and TiO2 nano-particles. The thermal stability of PANI/TiO2 nanorods improves with the contents of TiO2 increasing. The absorption of PANI/TiO2 nano-composites was found to be very intense in the range of violet and visible light by UV-Vis spectrum. The fluorescence of PANI/TiO2 nanorods was excited at 416 nm, and the intensity of fluorescence was strengthened greatly with increasing TiO2 concentration. The mechanism of the strengthened fluorescence quantum efficiency and fluorescence intensity of PANI/TiO2 was investigated through the charge transfer and exciton dissociation in PANI/TiO2 nanorods composites.