A new science strategy for natural fibre modification was devised in which glass surface properties would be imparted to wood-derived fibre. The enhancements known from addition of silane reagents to glass fibre–polymer composites could therefore be realised for modified cellulose fibre–polymer composites. A process is described whereby the internal void spaces and micropores of never-dried Kraft pulp fibre walls were impregnated with silica. This was achieved by initial dehydration of never-dried fibre through azeotropic distillation to achieve substitution of fibre water with the silicon chemical solution over a range of concentrations. Kraft fibres were stiffened and made resistant to collapse from the effect of the azeotrope drying. Specific chemical reaction of azeotrope-dried fibre with the reagent ClSi(OEt)3 followed by base-catalysed hydrolysis of the ester groups formed a fibre-bound silica composite. The physico-chemical substitution of water from micropores and internal voids of never-dried fibre with property-modifying chemicals offers possibilities in the development of new fibre characteristics, including fibres which may be hardened, plasticised, and/or stabilised against moisture, biodegradation or fire. The embedded silica may also be used as sites of attachment for coupling agents to modify the hydrophilic character of the fibre or to functionalise the fibre surface.