Photofermentative treatment of a dark fermentation effluent is investigated. Performances of a R. sphaeroides and a mixed PNSB culture are compared. The mixed culture results more efficient in H2 production (233.8 N mL H2 g COD−1). The pure culture shows a higher PHB productivity (155 mg PHB g COD−1). High soluble COD removal from DFE is achieved (>80%).