To overcome induced fatty acid inhibition during dark-fermentative hydrogen (H-2) production process, a hybrid strategy was designed and evaluated by co-culturing photosynthetic bacteria with acidogenic microflora. Augmented dark-photo fermentation system (ADPFS) illustrated 40% increment in cumulative H-2 production (CHP, 250 ml) compared to dark-fermentation system (DFS) along with 10% enhancement in COD removal efficiency. Co-culturing helped to reduce VFA accumulation by 40% which supports the functional role of photosynthetic organisms in reducing the fatty acid concentration in association to additional H-2 production. Relatively higher reduction in individual fatty acids viz., acetic acid (43%), butyric acid (57%) and propionic acid (65%) was observed with AD-PFS operation. Increment in bacteriochlorophyll (Bchl) after augmentation corroborated well with results. At lower pH, pheophytinization was observed which hindered H-2 production. Voltammograms illustrated dominant oxidation behavior during hybrid AD-PFS operation and provides viable option for enhancing performance by regulating system buffering microenvironment. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.