Bacteriopheophytin g and small amounts of bacteriochlorophyll g have been obtained in high purity from the recently discovered photosynthetic bacterium Heliobacterium chlorum. Preparative methods and precautions in handling these sensitive compounds are described. The compounds have been characterized by californium-252 plasma desorption mass spectrometry, HPLC, visible absorption, and electron spin resonance spectroscopy. Our results agree with the structure of bacteriochlorophyll g advanced by H. Brockmann and A. Lipinski [(1983) Arch. Microbiol. 136, 17-19], with the exception that we find the esterifying alcohol to be farnesol and not geranylgeraniol as originally suggested. Zero field splitting parameters of triplet state bacteriopheophytin g and the ESR properties of the cation free radical of bacteriochlorophyll g are reported. The photoisomerization of the subject compounds has been studied. Bacteriopheophytin g undergoes photo-isomerization in white light to pheophytin a with a half-time of approximately 42 min. We suggest that all of the chlorophylls are biosynthesized from a common intermediate containing an ethylidine group, [unk]CH-CH(3), such as is present in bacteriochlorophylls b and g.