Naturally occurring chlorophyllous pigments, which function as the cofactor in the early photochemical reaction of photosynthesis, have been proven beyond question to be magnesium-complexed porphyrin derivatives. Phototrophic organisms that use (bacterio)chlorophylls ([B]Chls) containing metals other than Mg were unknown for a long time. This common knowledge of natural photosynthesis has recently been modified by the striking finding that a novel purple pigment, zinc-chelated-BChl (Zn-BChl) a, is present as the major and functional pigment in species of the genus Acidiphilium. Acidiphilium species are obligately acidophilic chemoorganotrophic bacteria that grow and produce photopigments only under aerobic conditions. Although the mechanism of photosynthesis with Zn-BChl a in Acidiphilium species is similar to that seen in common purple bacteria, some characteristic photosynthetic features of the acidophilic bacteria are also found. The discovery of natural photosynthesis with Zn-BChl has not only provided a new insight into our understanding of bacterial photosynthesis but also raised some interesting questions to be clarified. The major questions are why the acidophilic bacteria have selected Zn-BChl for their photosynthesis and how they synthesize Zn-BChl and express photosynthetic activity with it in their natural habitats. In this article we review the current knowledge of the biology of Acidiphilium as aerobic photosynthetic bacteria with Zn-BChl a and discuss the interesting topics noted above.