Nature recruits various types of microbes to transform its waste products into reusable building blocks. In order to develop engineered systems to enable humans to generate useful products from complex sources such as biomass, a better understanding of the synergy between microbial species is necessary. Here we investigate a bioelectrochemical system for conversion of a complex biomass-derived pyrolysis stream into hydrogen via microbial electrolysis. Interaction between the exoelectrogens and fermentative organisms is key in this process. Comparing bioelectroconversion of a switchgrass-derived bio-oil aqueous phase (BOAP) with a model exoelectrogenic substrate, acetic acid, we demonstrate that fermentative breakdown of BOAP to acetate is the limiting step in the syntophic conversion process. The anode microbial community displayed simultaneous conversion of sugar derivatives, phenolic compounds, carboxylic acids, etc. present in BOAP, but at differing rates through division of labor and syntrophic exchange. Maximum removal for BOAP reached 43 mg COD/h vs. 59 mg COD/h for pure acetic acid. Furthermore, maximum hydrogen production for BOAP reached 11 L/L-d vs. 35 L/L-day for pure acetic acid. Coulombic efficiency for both substrates was >80%. Unpoising of the anode haulted exoelectrogenesis and allowed fermentative processes to proceed resulting in acetic acid accumulation at the rate of 8.4 mg/h. Coupled to the simultaneous conversion of compounds present within BOAP, these results support the division of labor and syntrophic interactions suggested here. The hydrogen productivity is the highest achieved to date for a biomass-derived stream. The exoelectrogenic rates achieved signify that commercial feasibility can be achieved if fermentative rates can be improved.