Syntheses and X‐ray structural characterizations of two new Cu(II) complexes Cu(tfbz)2(Htfbz)2(phen) (1) (Htfbz=2,4,5‐trifluorobenzoic acid, phen=1,10‐phenanthroline) and [Cu(pfbz)2(phen)]2(Hpfbz)2 (2) (Hpfbz=pentafluorobenzoic acid) are reported. The first complex crystallizes in the monoclinic space group C2/c with the crystal cell parameters a=1.9903(4) nm, b=1.3688(3) nm, c=1.3623(3) nm, β=97.90(3)°, V=3.6762(13) nm3 and Z=4. The second complex crystallizes in the triclinic space group P‐1 with the crystal cell parameters a=1.7965(4) Å, b=1.9236(2) Å, c=2.0916(2) Å, α=110.156(2) °, β=105.040(3) °, γ=98.123(3) °, V=6.3372(17) nm3 and Z=4. The crystallographic analyses revealed that F···H–C hydrogen bonds in both complexes lead to formation of infinite three‐dimensional supramolecular networks. A large number of F···F interactions in complex 2 ensure the stability of intricate crystal structure.