ZnO thin films were prepared by pulsed laser deposition on amorphous fused silica substrates at different ambient pressures varying from 0.5 to 500 mTorr, to observe the effect of ambient gas on their crystalline structure, morphology and optical properties. Results of X-ray diffraction, scanning electron microscopy, atomic force microscopy and photoluminescence studies showed that crystallinity, surface features and optical properties of the films significantly depended on the oxygen background pressure during growth. A low oxygen pressure (0.5 mTorr) seems to be suitable for the growth of highly c-axis oriented and smoother films possessing a superior luminescent property. The films grown at the higher pressures (50-500 mTorr) were found to have many defects probably due to an excessive incorporation of oxygen into ZnO lattice. We speculate that the film crystallinity could be affected by the kinetics of atomic arrangement during deposition at the higher oxygen pressures.