Four novel alkali-manganese(II) trifluoroacetates were synthesized, and their potential as self-fluorinating precursors to layered perovskites A(2)MnF(4) (A = K, Rb, and Cs) was demonstrated. Na2Mn(tfa)(4), K4Mn2 (tfa)(8), Rb4Mn2 (tfa)(8)center dot 0.23H(2)O, and Cs3Mn2 (tfa)(7)(tfaH) (tfa = CF3COO- and tfaH = CF3COOH) were grown as single crystals, and their crystal structures solved using X-ray diffraction. Chemically pure K4Mn2 (tfa)(8), Rb4Mn2 (tfa)(8)center dot 0.23H(2)O, and Cs3Mn2 (tfa)(7)(tfaH) were also prepared in polycrystalline form as confirmed by thermal analysis and powder X-ray diffraction. Thermolysis of these powders yielded the isostructural series K2MnF4, Rb2MnF4, and Cs2MnF4 at low temperatures (approximate to 200-300 degrees C). Trifluoromethyl groups belonging to the trifluoroacetato ligands served as the fluorine source, thereby eliminating the need for external fluorinating agents. K2MnF4 and Rb2MnF4 were obtained as single-phase powders, whereas Cs2MnF4 crystallized along with CsMnF3. Access to polycrystalline Cs2MnF4 coupled to Rietveld analysis enabled elucidation of the crystal structure of this ternary fluoride, which had remained elusive. Findings presented in this article expand the synthetic accessibility of polycrystalline A(2)MnF(4) fluorides, for which a scarce number of routes is available in the literature.