The $^1H-NMR$ signals of the heme methyl, propionate and related chemical groups of cytochrome $c_3$ from Desulfovibrio vulgaris Miyazaki F (D.v. MF) were site-specifically assigned by means of 1D-NOE, 2D-DQFCOSY and 2D-TOCSY spectra. They were consistent with the site-specific assignments of the hemes with the highest and second-lowest redox potentials reported by Fan et al. (Biochemistry, 29, 2257-2263 1990). The site-specific heme assignments were also supported by NOE between the methyl groups of these hemes and the side chain of Val-18.