A method for forming the alignment films on the substrate and a pixel structure of a liquid crystal display are disclosed. The pixel structure comprises a plurality of pixel units arranged in arrays. Each of the pixel units comprises a first substrate, a second substrate, two first alignment films and two second alignment films. The first alignment film is different from the second alignment film. The second substrate is disposed opposite to the first substrate. The two first alignment films and the two second alignment films are individually disposed on the first substrate and the second substrate, while each of the first alignment films is disposed substantially opposite to one of the second alignment films. The method for forming the alignment films comprises the following steps: (1) forming a trench on the substrate to divide each of the pixel units into a first sub-pixel area and a second sub-pixel area, (2) forming the first alignment film on the first sub-pixel area of the substrate and then, (3) forming a second alignment film on the second sub-pixel area of the substrate at last.