Novel luminescent silicone hybrids (LSHs) containing lanthanide ions were prepared via different sol–gel processes. The precursor, dimethyl ester-functionalized silane, was synthesized via a facile amino-ene reaction. The coordinated assembly of the ester ligands and lanthanide ions (Eu3+, Tb3+ and Dy3+) occurred. The ester ligands were immobilized onto the Si-O network backbone during the preparation of the silicone hybrid materials. The particle size can be controlled to ca 50 nm by adjusting the solvent ratio. The obtained materials were characterized by Fourier transform infrared, 1H nuclear magnetic resonance spectroscopy (NMR), 13C NMR, 28Si NMR, X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis, high-resolution scanning electronic microscopy and luminescent (excitation and emission) spectroscopy. The coordination state and photophysical performance of the compounds were studied in detail. The terbium- and europium-containing materials show sharp green and red emissions, respectively, which indicate that efficient intramolecular energy transfer took place in these LSHs.