Abstract Bridged polysilsesquioxanes (BPs) show great potential in the development of lanthanide‐based luminescent materials, owing to their capacity to loading lanthanide complexes with high concentration and their flexible processability. A novel BP precursor, consisting of a C 3 ‐symmetrical benzene central core moiety, capable of sensitizing the luminescence of Eu 3+ and Tb 3+ is reported. Tunable, full‐color luminescent gels were facilely prepared by mixing the as‐synthesized precursor and Ln 3+ ions in appropriate solvents. By either changing the Eu 3+ /Tb 3+ molar ratio or altering the excitation wavelength, the emission colors of the final gels can be finely tuned. Additionally, the yellow‐colored emissive gel with a molar ratio of Eu 3+ to Tb 3+ of 0.5 can be used as an effective ratiometric luminescent sensor for distinguishing amines with lower p K a (<5) from those with higher p K a (>9).