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Porous organosilica microparticles consisting of silane-derived cyclophosphazene bridges were synthesized by a surfactant-mediated sol-gel process. Starting from the substitution of hexachlorocyclotriphosphazene with allylamine, two different precursors were obtained by anchoring three or six alkoxysilane units, via a thiol-ene photoaddition reaction. In both cases, spherical, microparticles (size average of ca. 1000 nm) with large pores were obtained, confirmed by both, scanning and transmission electron microscopy. Particles synthesized