We have investigated the electronic structure of BiS2-based CeO0.5F0.5BiS2 superconductor using polarization-dependent angle-resolved photoemission spectroscopy (ARPES), and succeeded in elucidating the orbital characters on the Fermi surfaces. In the rectangular Fermi pockets around the X point, the straight portion parallel to the ky direction is dominated by Bi 6px character. The orbital polarization indicates the underlying quasi-one-dimensional electronic structure of the BiS2 system. Moreover, distortions on tetragonally aligned Bi could give rise to the band Jahn-Teller effect.