This article describes the synthesis, characterization, and reactivity of palladium(II) fluoride complexes containing sp2 and sp3 nitrogen-containing supporting ligands. Both cis and trans complexes of general structure (N)(N′)PdII(R)(F) (R = Ar or CH3) as well as cis-(N)2PdII(F)2 are reported. Crystallographic characterization of these molecules has allowed structural comparisons to related phosphine-ligated species. Furthermore, these studies have revealed that nitrogen-donor ligands support some of the longest and the shortest Pd–F bonds reported to date. The thermal decomposition of (N)(N′)PdII(R)(F) has also been examined, and no products of C–F bond-forming reductive elimination were obtained in any case.