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Abstract: Natively porous hybrid organic–inorganic sol–gel systems have been engineered to be used as functional positive photoresists, aimed to the realization of microsensors in a single-step process. Interesting results have been obtained combing three main sol–gel system features: the direct patternability through X-ray lithography, being processable without the addition of a photocatalyst; the functionalizability, properly designing the organic component of the hybrid network or incorporating active species; the open micro or mesoporosity, tailored by the synthesis process and precursor choice. The photoprocessable porous films have been synthesized starting from a Bridged Polysilsesquioxane (BPS) precursor, 1,4-bis(triethoxysilyl)benzene. The correlation between chemical properties of the sol–gel material and its patternability is described in detail. X-ray exposure leads to a progressive alkyl and aromatic compound elimination and promotes inorganic condensation in the system, allowing the selective dissolution of irradiated cross-linked films in suitable etchants. Patterns of final resolution lower than 100nm have been realized on BPS-based films synthesized in acid conditions, a procedure that allows to take advantage of a straightforward embedding protocol for active species in the sol–gel matrix. The BPS-based system has been doped with a covalently linked quinolinium dye, obtaining thin sensing films patternable by X-ray lithography. A feasibility test for the fabrication of optical microdevices, where fluorescence properties are obtained directly on the patterned coatings, has been provided. [Copyright &y& Elsevier]