The paper describes the preparation of a new photoluminescent silica aerogel by embedding a new Tb(III) complex in a silica matrix by using N-hydroxysuccinimide as ligand. The Tb(III) complex prepared at a metal to ligand ratio of 1:3 (mol%) exhibits strong photoluminescence as a result of specific radiative transitions within the Tb(III) cation with the most intense peak located at 543 nm due to 5D4 → 7F5 transition. The synthesized complex was doped in the silica matrix through a catalyzed sol–gel process. After ageing in ethanol, the alcogel was dried under supercritical regime by exchanging the ethanol with liquid carbon dioxide followed by supercritical evaporation. The leaching of the free complex from the alcogel during ageing and solvent exchange phases was found to be minimal most likely due to the interactions between chemical groups of complex with those specific to silica matrix. The obtained regular shaped monolithic aerogel preserved the remarkable photoluminescent properties and also improved the thermal stability of the free complex. Both, the free complex and doped aerogel were characterized through thermal analysis, FT-IR, powder X-ray diffraction, Scanning electron microscopy and fluorescence spectroscopy. For comparison purposes, an undoped silica aerogel was also prepared and investigated through FT-IR, BET analysis and powder X-ray diffraction. The excellent photoluminescent properties might recommend the prepared aerogel for applications in optoelectronic devices where photonic conversion materials are required.