A π-conjugated donor functionalized tris-dipicolinate complex, featuring promising two-photon excited luminescence properties in water was successfully embedded in a monolithic sol–gel material. A complete spectroscopic study unambiguously indicates that the europium complex conserves its integrity in this sol–gel matrix and the improvement of the luminescence lifetime clearly indicates a stabilisation of the complex in the matrix. Biphotonic confocal microscopy measurement shows that the Eu(III) luminescence can be sensitized in the sol–gel material using a two-photon antenna process, which is a first step towards the design of doped sol–gel nanoparticles for two-photon imaging applications.