Removal of the central metal from chlorophyll (Chl) molecules is biologically important in terms of production of the primary electron acceptors in photosystem-II photosynthetic reaction centers and the early stage in Chl degradation. The physicochemical properties on demetalation of chlorophyllous pigments are useful in the understanding of such reaction mechanisms in photosynthetic organisms. Here we analyzed the demetalation kinetics of a series of Zn-Chl derivatives with a systematic variation in the electron-withdrawing and -donating substituents at the 3-position of the chlorin macrocycle under acidic conditions to elucidate thoroughly the substitution effects on the demetalation properties of chlorophyllous pigments. Dehydrogenation of the aliphatic group (CH2CH3 --> CH=CH2 --> C CH) at the 3-position slowed the removal of the central zinc from the chlorin macrocycle. The gradual decrease in the demetalation rate constants of the three zinc chlorins originates from differences in the electron-withdrawing strength of the ethyl, vinyl, and ethynyl groups directly linked to the chlorin pi macrocycle. Reduction of the 3(1)-carbonyl groups significantly increased the demetalation rate constants, and the relative ratios of the demetalation rate constants of the zinc chlorins possessing a carbonyl group to those possessing the corresponding hydroxy group were analogous in the cases of 3-formyl- and 3-acetyl-zinc chlorins. The demetalation rate constants of the seven Zn-Chl derivatives possessing various electron-withdrawing and -donating groups exhibited good correlation with the Hammett sigma parameters of the 3-position substituents.