Organic-inorganic hybrids with controlled morphology at the nanometer scale represent an exciting class of materials that can display unique properties that are culminated by the characteristics of each building block. Recent research highlights their potential as biomimetic composites and application in biosensing, lab-on-chip devices, drug delivery and tissue engineering. Here we focus on the emerging class of biomaterials that integrate polymers with nanostructured porous silicon and emphasize the design of advanced 'smart' functions. Porous silicon is an appealing biomaterial due to the ease of tuning its many attractive properties, including pore morphology, photonic properties, biocompatibility, biodegradation and surface chemistry. An overview is presented of the principle concepts of design and fabrication of porous silicon-polymer hybrids. Current achievements in biomedical applications are reviewed and future prospects and challenges for healthcare technologies are discussed.