The electronic structure of zinc phthalocyanines ZnPc and ZnPcF16 is studied by X-ray emission and X-ray photoelectron spectroscopy methods. Experimental and theoretical parameters of the energy spectrum are analyzed along with the partial composition of highest occupied molecular orbitals (HOMOs) of the molecules of these compounds. It is shown that the frontier high-energy region of ZnPc HOMOs consists of 2pπ atomic orbitals (AOs) of nitrogens from non-equivalent groups (Nα, Nβ) and 2pπ orbitals of peripheral carbons (Cβγδ) with the participation of 3d orbitals of zinc which belong to both π (3dyz, 3dz2) and σ (3dxy) types. It is established that fluorine atoms and the central zinc atom in ZnPcF16 interact with each other by forming delocalized π orbitals with the participation of carbon pπ orbitals belonging to α, β, γ, δ groups as well as nitrogen pπ orbitals of α and β groups. The HOMO of ZnPcF16 consists mainly of 2px and 2py AOs of nitrogen (Nα and Nβ) and carbon (Cβ and Cγδ) with a small contribution of the 3dxz, yz orbital of zinc.