The Li alkoxide LiORF (1) (RF = C(CF3)3) was quantitatively prepared by reacting stoichiometric amounts of LiH and HORF. Upon reaction of 1 with 1 equiv of AgBF4, the first donor-free Ag(I) alkoxide AgORF formed in 86% yield. The Ag alkoxide was then used for the preparation of trigonal bipyramidal [(AgL)3(ORF)2]+ cage cations (L = C2H4 (3), C4H8 (4)) stabilized by weakly coordinating [Al(ORF)4]- counterions. 1 to 4 were characterized by multinuclear NMR, IR, and Raman spectroscopy as well as by their single-crystal X-ray structures and additional quantum chemical calculations.