Bioencapsulation in silica gels has become a very popular field of research, leading to the design of biosensors and bioreactors. If pure silica gels appear suitable to maintain the biological activity of entrapped enzymes, there are many cases where hybrid materials are necessary to reach the long-term preservation of biomolecular or cellular species and/or to provide new functionalities. This review focuses on the design of such nanocomposite materials combining silica with biopolymers. In the first part, the synthesis and characterization of these bio-hybrid materials are described, emphasizing the importance of the polymer influence on the reactivity of silica precursors. In the second part, the benefits of biopolymer incorporation in silica gels are illustrated in the context of biotechnological devices. As a conclusion, a parallel is drawn between biohybrids and biominerals, opening new perspectives for the design of multi-component biologically-active materials.