Color-tunable luminescent materials based on α, ω-diethyl malonate terminated polydimethylsiloxane (EP) and lanthanide ions are synthesized. The EP is synthesized from α, ω-hydride terminated polysiloxane (HP) and diethyl allyl malonate via hydrosilylation reaction. The FT-IR spectra, 1H NMR, 13C NMR, and GPC are used to characterize the structures of HP and EP. The obtained materials, which were synthesized by incorporating Eu3+ (or Tb3+) ions into EP, exhibit excellent narrow-width red (or green) emissions. Moreover, when integrating heterometallic Eu3+/Tb3+ ions into EP, the luminescence spectra of the complexes are composed of green and red emission. Color-tunable luminescent materials are obtained by tuning the proportions of Eu3+ and Tb3+ ions.