ZnO thin films have been prepared by pulse laser deposition technique at room temperatures (RT). These films were deposited on GaAs substrate to form the ZnO/GaAs heterojunction solar cell. The effect of annealing temperatures at ( RT,100, 200)K on structural and optical properties of ZnO thin films has been investigated. The X-ray diffraction analysis indicated that all films have hexagonal polycrystalline structure. AFM shows that the grains uniformly distributed with homogeneous structure. The optical absorption spectra showed that all films have direct energy gap. The band gap energy of these films decreased with increasing annealing temperatures. From the electrical properties, the carriers have n-type conductivity. From C-V measurement of ZnO/GaAs heterojunciton solar cell at frequency 100, 200 KHz, It is found that built–in potential (Vbi) increases with increase frequency. Also, from I-V characteristic it is observed that the ideality factor is 2.7. Short-circuit current (Isc) is 4.0mA/cm2, open circuit voltage (Voc) is 0.5V, fill factor ( F.F) is 0.7 and the efficiency is about 6.0 %.