The synergistic effect produced by functionalized ionic liquids in silica hybrid material for rare earth adsorption is presented for the first time in this article. Interestingly, distribution coefficient and synergistic enhancement coefficient of Lu(III) adsorbed by mixed [P-66614] [EHEHP] and [N-1888] [BTIAPP] in silica hybrid material (SHM) are pronouncedly higher than their individual contributions. The doped functionalized ionic liquids act as porogens and adsorbents in the SHM. Moreover, the structural difference of functionalized ionic liquids offers the possibility for their quantitative determinations, which is crucial for the investigation of synergistic effect from doped functionalized ionic liquids in the SHM. The synergistic interplay of functionalized ionic liquids is the key to the higher absorptivity of SHM for rare earth. Moreover, the synergistic effect of doped ILs in SHM is indicated to be stable for rare earth adsorption in five recycling. The elimination of third phase from ionic liquid is another remarkable advantage of the SHM over common extraction. Overall, the prepared SHM reveals efficient and sustainable potential for rare earth adsorption from a new perspective.