A kind of monomer (abbreviated as BrBAA-APES) was prepared by modifying 2-bromophenylacetic acid (BrBAA) with a coupling agent (3-aminopropyl) triethoxysilane (APES). Then it was used to coordinate to Tb3+ and to react with tetraethoxysilane (TEOS) in the presence of water molecules simultaneously. During the reaction, cohydrolysis and cocondensation occurred at the same time as complexation happened to Tb3+, which is called an in situ process. After 5 days, a kind of hybrid material was prepared. The hybrid exhibits the characteristic luminescence of Tb3+, and the change of the hybrid's excitation wavelength also testifies to the energy couple and intramolecular energy transfer between the triplet state energy of BrBBA-APES and emissive level of Tb3+.