To obtain porous TiO2 film, the precursor sol was prepared by hydrolysis of Ti isopropoxide and then complexed with trehalose dihydrate. The porous TiO2 film was fabricated by dip-coating technique on glass substrates using this solution. The TiO2 film was calcined at 500 °C. The maximum thickness of the film by one–run dip-coating was ca. 740 nm. The film was composed of nanosized particle and pore. The porosity of the TiO2 film was increased by the addition of trehalose dihydrate to the sol. The porous TiO2 films were calcined at various temperatures. The effects of the calcination temperature on the microstructure of the porous TiO2 film were investigated. The porous film prepared from sol containing trehalose still kept the porous structure for calcination at 950 °C. The phase transition temperature from anatase to rutile of the film was shifted from 650 to 700 °C by trehalose addition to the sol.