The work deals with the volatile asymmetric palladium complexes of β-ketoiminate-type as a new direction to design the effective partially fluorinated (O^N)-chelated precursors for metal–organic chemical vapor deposition (MOCVD). To determine the effect of the substituent on the donor nitrogen atom, [Pd(CF3COCHCN(R)CH3)2]2 complexes with R = CH3 (Mei-tfac) and N(CH3)2 (dmht) were synthesized and characterized by elemental analysis, IR and NMR spectroscopy. The molecular and crystal structures of the complexes as well as the initial ligand sources HMei-tfac and Hdmht were determined by single-crystal XRD. The obtained a new crystallographic and thermal (TG/DTA) information combined with the crystal lattice energy calculations allowed to reveal the features of the N-substituted fluorinated complexes in comparison with their non-fluorinated analogs. The possibility of using the proposed compounds as MOCVD precursors was experimentally confirmed.