A route for coordination of Eu3+ by dibenzoylmethane (DBM) covalently bonded inside hexagonal mesoporous silica was established here to produce the highly luminescent nanomaterial SiDBM-Eu(DBM)(2). Thermogravimetry, luminescence, X-ray diffraction, N-2 adsorption, FTIR, FrRaman, Si-29 NMR, and C-13 NMR in solid-state techniques were used to characterize SiDBM-Eu(PBM)(2). The Si-29 NMR spectrum proved that the DBM was covalently bonded to a silica framework. Thermogravimetric and titration data showed the 6.4 x 10(-2) mmol of Eu3+ per gram of silica, and each Eu3+ is coordinated by three DBMs in SiDBM-Eu(DBM)(2). SEM images confirmed that this material is formed by nanoaggregates with 200 nm diameter. N-2 adsorption isotherms showed the SiDBM-Eu(DBM)(2) complex with, 800 m(2) g(-1) and 6.4.,4 nm of porous diameter, characterizing mesoporosity of this nanomaterial. SiDBM-Eu(DBM)(2) showed an efficient DBM to Eu3+ intramolecular energy process, namely, antenna effect, which favored a highly luminescent behavior in this modified hexagonal mesoporous silica.