The synthetic strategies, structural comparison, and thermal gravimetric analyses for a novel family of alkaline earth metal perfluoro-tert-butoxides (PFTB) are presented. The isolated complexes follow the general formula, [Ae(PFTB)(2)(d)(x)]; (1a, Ae = Mg, d = THF, x = 2; 1b, Ae = Ca, d = THF, x = 4; 1c, Ae = Sr, d = THF, x = 4; 1d, Ae = Ba, d = THF, x = 4; 2a, Ae = Mg, d = DME, x = 1; 2b, Ae = Ca, d = DME, x = 2; 2c, Ae = Sr, d = DME, x = 2; 2d, Ae = Ba, d = DME, x = 3; 3a, Ae = Mg, d = diglyme, x = 1; 3b, Ae = Ca, d = diglyme, x = 2; 3c, Ae = Sr, d = diglyme, x = 2; 3d, Ae = Ba, d = diglyme, x = 2; THF = tetrahydrofuran, DME = 1,2-dimethoxyethane) where the crystallographically characterized compounds display either a cis or trans conformations in octahedral or pseudo-octahedral environments. Alkane elimination (Mg), direct metalation via ammonia activation (Ca, Sr, Ba), and transamination (Ca, Sr, Ba) methods yielded the target compounds in moderate to good yields. Structural studies of select compounds showed all compounds to be monomeric with varying degrees of co-ligand coordination, possibly explaining some of the observed physical properties. Thermal gravimetric analyses of the compounds shows sublimation at low temperatures, associated with minimal residue, making this family of fluoroalkoxides promising candidates for metal organic chemical vapor deposition (MOCVD).