Increasing the power conversion efficiency (PCE) of silicon solar cells by improving their junction properties or minimizing light reflection losses remains a major challenge. Extensive studies were carried out in order to develop an effective antireflection coating for monocrystalline solar cells. Here we report on the preparation of a nanostructured cerium oxide thin film by pulsed laser deposition (PLD) as an antireflection coating for silicon solar cell. The structural, optical, and electrical properties of a cerium oxide nanostructure film are investigated as a function of the number of laser pulses. The X-ray diffraction results reveal that the deposited cerium oxide films are crystalline in nature and have a cubic fluorite. The field emission scanning electron microscope investigations show an increase in the film grain size with increasing the number of laser pulses. The carrier concentration of the film decreases and the mobility increases as the number of laser pulses increases. The cerium oxide film deposited on silicon at 900 laser pulses exhibits a minimum optical reflection. The maximum PCE was 19.27% and fill factor of 87% was obtained after the deposition of silicon solar cell with cerium oxide nanostructured film deposited at 1000 laser pulses.