A procedure for the chemical immobilization of a new ZnII-EuIII heterobimetallic complex in the SiO2 aerogel matrix has been developed. In this Zn-Eu complex, a peripheral non-luminescent Zn ion acts as a binder to a silica matrix and prevents direct interaction of rare-earth ions with OH– and NH– groups in the silica matrix which would have a detrimental effect on the luminescence of lanthanides. The procedure includes the synthesis of complexes, co-gelation of the obtained complex with SiO2 sol, the washing of lyogels and their subsequent supercritical drying in CO2. The composition and properties of the obtained aerogels were investigated using a low-temperature nitrogen adsorption technique, helium pycnometry, FTIR, Raman, UV–visible and luminescence spectroscopy, XPS, PXRD, SEM, TEM, TGA combined with mass spectrometry and small-angle neutron scattering. The aerogels modified with the ZnII-EuIII complex demonstrated strong red luminescence upon excitation with UV light.