In this study, a Q-switched Nd:YAG laser with specific parameters, including a pulse repetition rate of 6 Hz, a pulse duration of 10 nm, a wavelength of 532 nm, and a laser fluence of 237.47 J cm−12, was employed to fabricate highly crystalline TiO2 nano-films. These nano-films exhibited a narrow energy band gap of 3.24 eV and showcased favorable surface morphology, characterized by a roughness of 2.38 nm. A solar cell device was produced by creating porous silicon (PSi) and applying titanium dioxide films onto the PSi, achieving a notable conversion efficiency of 8.733%. To investigate the impact of different parameters on the resulting TiO2 nano-films, a range of laser fluences (ranging from 131.93 to 263.85 J cm−12) and three distinct laser wavelengths (1064 nm, 532 nm, and 355 nm) were employed during the pulsed laser deposition (PLD) process. These experiments aimed to grow TiO2 films on both quartz and silicon (Si) substrates.