Very recently, the exploitation of oxidic networks derived from sol–gel processes for the surface modification of natural and/or synthetic fibres/fabrics has been successfully assessed, giving rise to novel “green” flame retardant systems. Indeed, inorganic, doped and hybrid organic–inorganic architectures can significantly improve the thermal stability and flame retardancy of the treated textile substrates, notwithstanding their functional (i.e. antimicrobial, self-cleaning, UV-protection, …) features. The present paper aims to describe the state of the art, the current academic efforts and the perspectives on the use of sol–gel derived hybrid architectures as effective flame retardant systems.