Complicated structures where oxygen and fluorine are found together in one framework, where deviations from Pauling's second crystal rule (PSCR) are expected, often result in structures with important physical properties. The [NbOF5](2-) anion and therefore all the individual Nb-O and Nb-F bonds are ordered in noncentrosymmetric KNaNbOF5 and centrosymmetric CsNaNbOF5. The Na/K- and Na/Cs-O/F interactions in these phases, in particular the expected deviations from PSCR and the bond valence model, reveal the essential role of the small potassium cations in the acentric packing of the [NbOF5](2-) anion. KNaNbOF5 crystallizes in the orthorhombic and polar space group Pna2(1) (No. 33) with lattice constants a = 11.8653(11) angstrom, b = 5.8826(6) angstrom, c = 8.1258(8) angstrom, and Z = 4, while CsNaNbOF5 crystallizes in the orthorhombic space group Pbcn(No. 60) with lattice constants a = 8.3155(7), b = 13.3176(11), c = 11.1314-(9), and Z = 8.