The synthesis of novel metal-free and magnesium porphyrazines, peripherally substituted with dithia-dioxa (S2O2) and tetrathia (S-4) 14-membered macrocycles were performed by cyclotetramerization of (6Z)-1,3,4,9,10,12-hexahydro-2,5,8,11-benzo-dioxadithiacyclotetradecine-6,7-dicarbodinitrile (3) or (6Z)-1,3,4,9,10,12-hexahydro 2,5,8,11-benzotetrathiacyclotetradecine-6,7-dicarbodinitrile (5). The metal-free porphyrazines have been obtained by known route. The structure of compounds were characterized by elemental analysis and H-1, C-13 NMR, IR, UV-vis, and MS spectral data. The solvent extraction properties of the synthesized compounds towards some metal cations, such as Ag(I), Hg(II), Cu(II), Mn(II), Cr(III), Ni(II), Pb(II), and Zn(II) have been investigated. The effect of Cu2+, Mn2+, Ni2+, Pb2+, Sr2+, Al3+, Zn2+, Ba2+, Cd2+, Co2+, Hg2+, and Ag+ ions on the absorption spectra of the compounds were investigated by means of spectrophotometric method. Magnesium porphyrazine with S2O2 (6) interacted within Hg2+ ion specifically of all the tested metal ions.