The synthesis, crystal structure, and electronic properties of perfluoro-isopropyl-substituted perfluorophthalocyanine bearing a copper atom in the central cavity (F64PcCu) are reported. While most halogenated phthalocyanines do not exhibit long-term order sufficient to form large single crystals, this is not the case for F64PcCu. Its crystal structure was determined by X-ray analysis and linked to the electronic properties determined by electron paramagnetic resonance (EPA). The findings are corroborated by density functional theory (DFT) computations, which agree well with the experiment. X-band continuous-wave EPR spectra of undiluted F64PcCu powder, indicate the existence of isolated metal centers. The electron-withdrawing effect of the perfluoroalkyl (R-f) groups significantly enhances the complexes solubility in organic solvents like alcohols, including via their axial coordination. This coordination is confirmed by X-band H-1 HYSCORE experiments and is also seen in the solid state via the X-ray structure. Detailed X-band CWEPR, X-band Davies and Mims ENDOR, and W-band electron spin-echo-detected EPA studies of (FPcCu)-Pc-64 in ethanol allow the determination of the principal g values and the hyperfine couplings of the metal, nitrogen, and fluorine nuclei. Comparison of the g and metal hyperfine values of F64PcCu and other PcCu complexes in different matrices reveals a dominant effect of the matrix on these EPA parameters, while variations in the ring substituents have only a secondary effect. The relatively strong axial coordination occurs despite the diminished covalency of the C-N bonds and potentially weakening Jahn-Teller effects. Surprisingly, natural abundance C-13 HYSCORE signals could be observed for a frozen ethanol solution of F64PcCu. The C-13 nuclei contributing to the HYSCORE spectra could be identified as the pyrrole carbons by means o(4) DFT. Finally, F-19 ENDOR and easily observable paramagnetic NMR were found to relate well to the DFT computations, revealing negligible isotropic hyperfine (Fermi contact) contributions. The singlesite isolation in solution and solid state and the relatively strong coordination of axial ligands, both attributed to the introduction of R-f groups, are features important for materials and catalyst design.