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Abstract Anionic molecular models for nonhydrolyzed and partially hydrolyzed aluminum and gallium framework sites on silica, M[OSi(OtBu)₃]₄⁻and HOM[OSi(OtBu)₃]₃⁻(where M=Al or Ga), were synthesized from anionic chlorides Li{M[OSi(OtBu)₃]₃Cl} in salt metathesis reactions. Sequestration of lithium cations with [12]crown‐4 afforded charge‐separated ion pairs composed of monomeric anions M[OSi(OtBu)₃]₄⁻with outer‐sphere [([12]crown‐4)₂Li]⁺cations, and hydroxides {HOM[OSi(OtBu)₃]₃} with pendant [([12]crown‐4)Li]⁺cations. These molecular models were characterized by single‐crystal X‐ray diffraction, vibrational spectroscopy, mass spectrometry and NMR spectroscopy. Upon treatment of monomeric [([12]crown‐4)Li]{HOM[OSi(OtBu)₃]₃} complexes with benzyl alcohol, benzyloxide complexes were formed, modeling a possible pathway for the formation of active sites for Meerwin–Ponndorf–Verley (MPV) transfer hydrogenations with Al/Ga‐doped silica catalysts.