Nanostructured porous silicon (nPSi) is a nanostructured biomaterial which has received considerable attention in biomedical applications due to its biocompatibility, biodegradability, high surface area, and the ease to modify its surface chemistry. In the present work, nPSi composite microparticles are evaluated as potential drug delivery system. nPSi layers are formed by electrochemical etching of silicon wafers in hydrofluoric acid solutions. This fabrication process allows modifying the main properties of nPSi layers, including the porosity, average pore size and pore shape, by simply controlling the main parameters in the process, such as the applied current density and the electrolyte composition. nPSi microparticles are prepared from the removal and fracture by ultrasound sonication of nPSi layers. Composites are obtained from oxidized nPSi (nPSi-Ox) microparticles cascade processed with chitosan (CHI) and β-cyclodextrin (βCD) biopolymers. Samples are evaluated as drug delivery system using florfenicol (FF) as model drug, due to its economical and sanitary importance in salmon industry. Drug loaded and release kinetic tests are performed in different media: distilled water and simulated seawater. Initial data show that nPSi–βCD composites allow a mayor control in the drug time release kinetic compared to nPSi-Ox microparticles.