Despite their excellent flame retardant properties, polyphosphazenes are currently not used as flame retardant agents for textile finishing, because a permanent fixation on the substrate surface has failed so far. Here, we present the successful synthesis and characterization of a noncombustible and foam-forming polyphosphazene derivative, that can be immobilized durably on cotton and different cotton/polyester blended fabrics using photoinduced grafting reactions. The flame retardant properties are improved, a higher limiting oxygen index is found, and the modified textiles pass several standardized flammability tests. As flame retardant mechanism a synergistic effect between the immobilized polyphosphazene and the textile substrate was observed. The polyphosphazene finishing induces an earlier decomposition of the material with a reduced mass loss in thermogravimetric analysis. The decomposition of cotton and polyester leads to the formation of phosphorus oxynitride, which forms a protecting barrier layer on the fiber surface. In addition, the permanence of the flame retardant finishing was proven by laundry and abrasion tests.