In this study, furanic and phenolic compounds are problematic byproducts resulting from the decomposition of lignocellulosic biomass during biofuel production. This study assessed the capacity of a microbial electrolysis cell (MEC) to produce hydrogen gas (H<
sub>
2<
/sub>
) using a mixture of two furanic (furfural, FF
5-hydroxymethyl furfural, HMF) and three phenolic (syringic acid, SA
vanillic acid, VA
and 4-hydroxybenzoic acid, HBA) compounds as the sole carbon and energy source in the bioanode. The rate and extent of biotransformation of the five compounds, efficiency of H<
sub>
2<
/sub>
production, as well as the anode microbial community structure were investigated. The five compounds were completely transformed within 7-day batch runs and their biotransformation rate increased with increasing initial concentration. At an initial concentration of 1,200 mg/L (8.7 mM) of the mixture of the five compounds, their biotransformation rate ranged from 0.85 to 2.34 mM/d. The anode coulombic efficiency was 44-69%, which is comparable to wastewater-fed MECs. The H<
sub>
2<
/sub>
yield varied from 0.26 to 0.42 g H<
sub>
2<
/sub>
-COD/g COD removed in the anode, and the bioanode volume-normalized H<
sub>
2<
/sub>
production rate was 0.07-0.1 L/L-d. The major identified fermentation products that did not transform further were catechol and phenol. Acetate was the direct substrate for exoelectrogenesis. Current and H<
sub>
2<
/sub>
production were inhibited at an initial substrate concentration of 1,200 mg/L, resulting in acetate accumulation at a much higher level than that measured in other batch runs conducted with a lower initial concentration of the five compounds. The anode microbial community consisted of exoelectrogens, putative degraders of the five compounds, and syntrophic partners of exoelectrogens. The H<
sub>
2<
/sub>
production route demonstrated in this study has proven to be an alternative to the currently used process of reforming natural gas to supply H<
sub>
2<
/sub>
needed to upgrade bio-oils to stable hydrocarbon fuels.