Zn0.99Fe0.01O thin films on Al2O3 substrates are successfully prepared by using pulsed laser deposition(PLD) technique.And the influence of annealing oxygen pressure on the crystal structure and laser-induced voltage (LIV) effect of Zn0.99Fe0.01O thin films is studied. X-ray diffraction (XRD) analysis shows that Zn0.99Fe0.01O thin films are hexagonal wurtzite structure and ［001］ orientation. Meanwhile, with annealing oxygen pressure increasing, the grain size D of Zn1-xFexO thin films first increases and then decreases. At annealing oxygen pressure of 2000 Pa, the grain size D of Zn1-xFexO thin films achieves maximum, and crystallization quality is the best. In addition, at annealing oxygen pressure of 3000 Pa, the largest LIV signal of 79.5 mV is measured in Zn0.99Fe0.01O films grown on 10° vicinal-cut Al2O3 single crystal substrates.