An innovative method for Si nanostructures (NS) fabrication is proposed, through nanosecond laser irradiation (λ = 532 nm) of thin Si film (120 nm) on quartz. Varying the laser energy fluences (425–1130 mJ/cm2) distinct morphologies of Si NS appear, going from interconnected structures to isolated clusters. Film breaking occurs through a laser-induced dewetting process. Raman scattering is enhanced in all the obtained Si NS, with the largest enhancement in interconnected Si structures, pointing out an increased trapping of light due to multiple scattering. The reported method is fast, scalable and cheap, and can be applied for light management in photovoltaics.