Thermochemical processing is a promising method for the rapid depolymerization of biomass. This study investigated switchgrass, corn stover, red oak, hybrid poplar, and loblolly pine in terms of heteropolymer and elemental composition, and the distribution and composition of the fast pyrolysis products. Corn stover differed from other biomass types in that less of the biomass was recovered as sugar or phenolic oil (PO) and more of the biomass was recovered as bio-char and bio-gas. The sugar-rich aqueous stream recovered from the bio-oil heavy fraction was characterized in terms of sugar content and distribution, inhibitor content, and ability to support production of ethanol by Escherichia coli KO11 + lgk as a model biorenewable product. Levoglucosan was the most abundant sugar from each type of biomass, followed by either xylose or cellobiosan. For hybrid poplar, cellobiosan accounted for 30 wt% of the total sugar pool. Each of the sugar streams also contained a variety of inhibitors, particularly 5-hydroxymethylfurfural (5-HMF) and methylcyclopentenolone. Methylcyclopentenolone, maple lactone, was found to decrease the specific growth rate of E. coli by 50% when present at 0.72 wt%, indicating that it is less toxic than furfural, acetic acid and guaiacol. Sugars produced from switchgrass contained 4-fold less contaminants on a per-sugar basis than those from poplar and pine. All of the sugar streams contained too many inhibitors to be used at an industrially feasible concentration without additional detoxification. The poplar-derived pyrolytic sugar syrup was particularly inhibitory, possibly due to the high abundance of aromatic hydrocarbons, such as xylenes, and anisoles.