Density functional theory (DFT) calculations are performed on a series of peripherally substituted free-base and fluorinated zinc phthalocyanines, namely FnPcM (M = 2H, Zn; n = 16, 32, 48, 64). F16PcM, F32PcM, and F48PcM all prefer a planar skeletal structure of the metallomacrocycle core. In the case of F64Pc, F64PcZn remains planar but F64PcH2 is domed. The occurrence of a dome distortion appears to be related, at least in part, to the orientation of the isopropyl -C3F7 substituents as well as to the intermolecular (packing) interactions. The trends in the calculated results of the Pc2-–M2+ binding energy, polarizabilities, and electron excitation energies in H16PcM, F16PcM, and F64PcM are in agreement with the experimental observations, as are the geometrical features. It is further confirmed that the simpler F32PcM or F48PcM mimic the basic electronic properties of F64PcM.