Evidence is presented which points to (at least) two bound forms of bacteriochlorophyll present in chromatophores of Rhodospirillum rubrum, both of them readily converted to unbound bacteriochlorophyll (abs. max. 770 mu) when the chromatophores are extracted with acetone or ethanol. Controlled oxidation of the chromatophores with Ir(IV) or with Zn(II) and ferricyanide preferentially destroys the more strongly absorbing pigment (abs. max. 880 mu) but brings about only a slight decrease in the magnitude of the photoinduced absorption changes at 810 and 792 mu. Such oxidations yield a new pigment, absorbing at 715 mu in the aqueous preparation and, more strongly, at 680-684 mu when the pigment is extracted into organic solvents. This pigment is formed irreversibly and is therefore different from the material formed by photooxidation of chromatophores. Its visible spectrum and the spectrum of the material formed from it by acidification suggest that it is a chlorophyll-like substance, possibly derived from bacteriochlorophyll by (two-electron) oxidation of one of the dihydropyrrole rings to a pyrrole ring. Directions are given for separation of this pigment from other colored compounds present in the oxidation mixtures.