Nanostructured photodetectors have garnered great attention due to their enriched electronic and optical properties. In this work, we aim to fabricate a high-performance CeO2/Si photodetector by growing a CeO2 nanostructure film on a silicon substrate using the pulsed laser deposition (PLD) technique at different laser energy densities. The impact of laser energy density and the number of pulses on the morphological, optical, and electrical properties was studied. Field emission scanning electron microscopy (FESEM) results show that the CeO2 film has a spherical grain morphology with an average grain size ranging from 33 to 54 nm, depending on the laser energy density. The film deposited at various numbers of laser pulses also has spherical grains with an average grain size ranging from 39 to 54 nm, depending on the number of pulses. The optical properties of the CeO2 film showed that the optical energy gap of the films decreased from 3.5 to 3 eV as the laser energy density increased from 63.66 to 101.86 J/cm2. The photoluminescence (PL) spectra of the nanostructured CeO2 film reveal that the main emission peaks were observed at 682 nm when excited at 450 nm. The effect of laser energy density on the electrical properties, including carrier concentration, mobility, and current-voltage characteristics under dark and illuminated conditions, was investigated. The CeO2/Si photodetector fabricated at 63.66 J/cm2 showed the highest responsivity of 0.69 A/W at 450 nm, detectivity as high as 1.5 × 1010 Jones at 450 nm, and an external quantum efficiency of 92% when biased to 5 V. The photodynamic response time was measured