The clean and ordered surfaces of CdZnTe (111)B grown by the Bridgman method were obtained by Ar ion bombardment and thermal annealing in situ in an ultrahigh vacuum. The surface atomic structures of CdZnTe (111)B after annealing at different temperature were observed by low-energy electron diffraction (LEED). The valence band and work function of CdZnTe (111)B surfaces were determined by synchrotron radiation photoemission spectroscopy. The order of CdZnTe (111)B after annealing at 350 °C will worsen, and the (111)B-(2 × 2) local reconstruction will be formed. The work function of CdZnTe (111)B after annealing at 350 °C is 0.8 eV higher than that of CdZnTe (111)B-(1 × 1), and the local reconstruction may be induced by Te adatoms on top of the ideal truncation.