Modern trends in optical bioimaging require novel nanoproducts combining high image contrast with efficient treatment capabilities. Silicon nanoparticles are a wide class of nanoobjects with tunable optical properties, which has potential as contrasting agents for fluorescence imaging and optical coherence tomography. In this paper we report on developing a novel technique for fabricating silicon nanoparticles by means of picosecond laser ablation of porous silicon films and silicon nanowire arrays in water and ethanol. Structural and optical properties of these particles were studied using scanning electron and atomic force microscopy, Raman scattering, spectrophotometry, fluorescence, and optical coherence tomography measurements. The essential features of the fabricated silicon nanoparticles are sizes smaller than 100 nm and crystalline phase presence. Effective fluorescence and light scattering of the laser-ablated silicon nanoparticles in the visible and near infrared ranges opens new prospects of their employment as contrasting agents in biophotonics, which was confirmed by pilot experiments on optical imaging.