The surface electronic structures of conjugated regio regular and regio random poly (3- hexylthiophene) (rr-P3HT and rra-P3HT) thin films were studied by near edge X-ray absorption fine structure spectroscopy, ultraviolet photoelectron spectroscopy and Penning ionization electron spectroscopy (PIES). The distribution of the surface electronic states was controlled on rr-P3HT and rra-P3HT thin films with different molecular ordering by varying the coating process and PIES was adopted to observe the electronic states existing outside the surface.