This paper reports structural, morphological, optical and humidity sensing characteristics of pulsed laser deposited ZnO film. The XRD pattern reveals amorphous structure of the film. Scanning electron micrograph indicates formation of ZnO rods in micron size. Transmission increases gradually in the UV-VIS region. For studying the humidity sensing characteristics of the film, base of a right angled isosceles glass prism has been coated. Chopped light from a polarized He-Ne laser incident on the entry face of the prism gets reflected from the base – film – humid air interfaces and then emergent light is collected by the detector placed in front of the exit face of the prism. The least change in relative humidity which could be measured using the present configuration is 1.06RH%. Further the film is annealed at 400°C for four hours and its humidity sensing behavior is investigated in the similar manner which now shows a reversed trend. The sensitivity to humidity has decreased and the least change which could be detected now is 1.16RH%.