The formation and the luminescence behavior of the Eu(TTFA)(3) sol-gel films have been investigated. The Thenoyltrifluoroacetone (TTFAH) was dissolved in ethanol in advance, and then the EuCl3 and ethanol containing TTFAH were introduced into the initial precursor sol. The precursor sol was dip-coated onto substrates to form Eu(TTFA)(3) doped sol-gel films. The luminescence intensity of the Eu(TTFA)(3) doped sol-gel films was significantly increased with the increase of film thickness. However, there existed an efficient luminescence layer in the Eu(TTFA)(3) doped sol-gel films. The luminescence intensity did not increase when increasing the film thickness above the thickness of the efficient luminescence layer. The thickness of the efficient luminescence layer was related to the Eu(TTFA)(3) concentration in the film. The higher the Eu(TTFA)(3) concentration, the thinner the efficient luminescence layer. The heat treatment temperature of the films had also influence on the luminescence intensity. With the increase of the temperature, the Eu(TTFA)(3) formed gradually and luminescence intensity increased. But when the temperature was higher than 150 degrees C, the luminescence intensity decreased rapidly due to the decomposition of the Eu(TTFA)(3).