The cesium triorganofluorometalates [Cs{R(3)MF}](4) (1, M = Ga, R = Et; 2, M = Ga, R = i-Pr; 3, M = In, R = Et; 4, M = in, R = i-Pr) have been prepared by the reaction of the corresponding group 13 metallanes GaEt(3), Ga(i-Pr)(3), InEt(3), and In(i-Pr)(3) with CsF in acetonitrile. 1-4 have been fully characterized by elemental analysis, and IR, NMR, and MS techniques. The crystal structures of 2 and 4 have been determined. 2 and 4 are isostructural and crystallize in the cubic space group I23, with a = 1396.3(1) pm, V = 2722.3(5) x 10(6) pm(3), Z = 2, and R(1) = 0.0168 (wR(2) = 0.0343) for 2 and a 1417.1(2) pm, V = 2845.8(6) x 10(6) pm(3), Z = 2, and R(1) = 0.0166 (wR(2) = 0.0354) for 4. The structures of 2 and 4 display strongly distorted cubes with alternating cesium and fluorine atoms and can be described as (CsF)(4) subunits of the CsF structure stabilized by M(i-Pr)(3) groups. According to the analytical and spectroscopic data, 1 and 3 also possess Cs-F heterocubane structure.