Mononuclear copper(II) complexes were synthesized based on fluorinated diketonates decorated with a carbonyl or acetal group. The X-ray diffraction data demonstrate the effect of the nature of the fluorinated substituent on the crystal structure of homoleptic copper(II) complexes. As opposed to 1,2,4-triketonate, the acetal moiety of 1,3-diketonate enables intermolecular coordination to the metal centers, thereby making it possible to use 1,3-diketonate in further synthesis of heterometallic structures.