In order to enhance the intensity of luminescent hybrid bimodal mesoporous silica (LHMS), the rare earth Eu 3+ ion was employed as an enhancer to modify 1,8-naphthalic anhydride (NA) molecules. The modified LHMS were prepared with various anions of europium salts including Cl − , NO 3 − , and CH 3 COO − . The structure and photoluminescence properties of the obtained samples were characterized by XRD, TEM, N 2 -adsorption/desorption, FT-IR, TGA, ICP-OES, and PL measurements. The results showed that the bimodal mesoporous system of BMMs could be preserved after functionalization via grafted Eu 3+ -modified NA molecules onto mesoporous matrix. However, the structure parameters and textural properties of resultant LHMS series were obviously influenced by the anions volume. Meanwhile, the luminescent performances of LHMS series were seriously impacted by both of the binding force between Eu 3+ and various anions and steric hindrance of the anions, resulting in the intensity of emission peak of obtained LHMS series declining as following order: LHMS-EN (NO 3 − ) > LHMS-EA (CH 3 COO − ) > LHMS-EC (Cl − ). Finally, the related mechanism was discussed in-depth.