The migration behavior of aryl-substituted porphyrins and their metalloporphyrins with Zn(II), Ni(II), and Cu(II) were studied in high-performance thin-layer chromatography systems with silica gel and RP(18) plates using different organic mobile phases having different polarities. The (bromohydroxy)phenyl, (phenoxy)phenyl, and oxy(acetic acid)phenyl porphyrins migrated at similar rate. Chloromethylphenylporphyrin was weakly adsorbed on silica gel using either polar or nonpolar mobile phases. The mobility of metal complexes generally tends to increase in the given order of central metal ions: Zn(II) < Ni(II) < Cu(II) on silica gel. The favorable mobile phase for the separation of ligands and the metalloporphyrins is a mixture of acetonitrile-benzene.