A porphyrin compound of the formula: ##STR1## wherein R.sub.1 and R.sub.2 are each --CH.dbd.CH.sub.2, --CH.sub.2 CH.sub.3, --CH(O-lower alkanoyl)CH.sub.3, --CH(OR)CH.sub.3 or --CH(O-lower alkylene-OR)CH.sub.3 ; R.sub.3 is --H, --COOH, --COO-lower alkyl, --COO-lower alkylene-OR or --COO-lower alkylene-OOC-Z; R.sub.4 is --H, -lower alkyl or -lower alkylene-OR; R is --H, -lower alkyl or a residue of a polyfunctional carboxyl compound excluding a hydrogen atom therefrom; Z is a residue of the compound of the formula (I) excluding R.sub.3 therefrom; A is --CH.sub.2 -- or --CO--; and the dotted line from the gamma-position indicates no bonding or a single direct bond; and the dotted line between the 7- and 8-positions indicates the presence of a single bond or a double bond; and its complexes with a metal(s) in the porphine skeleton and/or at the residue of the polyfuntional carboxyl compound, at least one of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 being a group containing R which represents the residue of the polyfunctional carboxyl compound and R.sub.1 being capable of representing 1-iodoethyl in addition to said meanings when R.sub.3 is --COO-lower alkylene-OOC-Z, which shows a high accumulation in the locus of cancer with quick excretion from normal tissues.