The present invention relates a technique of liquid crystal display, especially to an alignment film applied to a substrate of a liquid crystal display. The alignment film includes a plurality of alignment molecules including polyamic acid and/or polyimide and a plurality of photo-sensitive molecules including terphenyl and/or substituted terphenyl, wherein a mass ratio of the plurality of alignment molecules to the plurality of photo-sensitive molecules is 3˜7%:0.0002˜2%. The present invention further provides a method of fabricating the alignment film and a liquid crystal display using the same. Due to the photosensitive group of the monomers, the plurality of alignment molecules can be formed with an appropriated rate, and the alignment film formed thereby has homogeneity. Therefore, the optic quality and overall performance of the liquid crystal display are enhanced.