Thin film with immobilized particulates of Cobalt oxide (Co3O4) has been synthesized by Pulsed Laser Deposition (PLD) technique followed by thermal treatment in air. Surface morphology of the Co3O4 films was examined using Field Emission Scanning Electron Microscopy (FESEM). Crystalline structure of Co3O4 films was investigated by X-ray Diffraction (XRD) and Raman spectroscopy was used to confirm the presence of Co3O4 phase on the surface. Efficient catalytic performance was obtained with these films for hydrolysis in Sodium Borohydride (NaBH4). A maximum hydrogen generation rate of ~5100 mL min -1 g -1 of catalyst was recorded at a temperature of 305 K with calculated activation energy of 62.96 kJ/mol. Good catalytic activity could be attributed to nanostructures of the films formed following heat treatment consisting of densely packed nanoparticles (NPs) which act as active catalytic centers, and the immobilized nature of the particles on the surface of the films. These catalyst films showed no major loss of activity even after five cycles of use allowing at the same time an advantage of easy separation from the solution. Our results thus demonstrate good catalytic performance and reusability of such PLD deposited Co3O4 nanostructured films towards hydrogen production by hydrolysis of NaBH4.