The invention discloses a method for self assembling non-spherical polystyrene grains to form into a multihole and ordered structure, which comprises the following steps of: firstly preparing a core shell type solid crosslinked polystyrene microballoon with single dispersed cross linking degree which is more than 10%; putting the microballoon into organic solvent I with the parameter of solubility which is 8.0-9.5 to remove cores which are not be cross linked in a dissolving way; obtaining a hollow crosslinked polystyrene microballoon by means of solid-liquid separation; and dispersing the hollow crosslinked polystyrene microballoon in an organic solvent II which has the density ratio which is smaller than the organic solvent I and the boiling point which is smaller than 80 DEG C, and can plastify the polystyrene to form into suspending liquid, and dropping the suspending liquid on a substrate to dry at the constant temperature of 24-50 DEG C for 5-10h. The method solves the problem of the directed orientation of non-spherical grains in the current product, can complete the transformation from the hollow crosslinked polystyrene microballoon to the non-spherical grains, the self assembly of the grains and the directed orientation of the grains for once, can control the shapes of the grains according to the self-assembly temperature, and is a simple and effective method for preparing the multihole and ordered structure.