Organic/inorganic heterojunctions have been fabricated by spin coating p-type poly (3, 4 ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS) onto n-type zinc oxide (ZnO) films. The ZnO films were deposited onto indium tin oxide (ITO) coated glass by pulse laser deposition (PLD) technique. The current density-voltage (J-V) characteristics of the PLD-ZnO/PEDOT:PSS junction based on as-deposited PLD-ZnO film shows a good rectifying behavior with a rectification ratio of 156 at ±1 V, indicating the formation of a diode between ZnO and PEDOT:PSS. Using thermionic emission model, the ideality factor (n=2.1) and barrier height (0.66 eV) of the heterojunction were obtained. Those diode parameters are better than those of the chemical vapor deposited ZnO/PEDOT:PSS heterojunction reported elsewhere, indicating that PLD may be a promising technique on fabricating high quality ZnO/polymer heterojunctions.