Hydrogen can be obtained from biomass pyrolysis liquids by catalytic steam reforming. Catalyst deactivation by coking and the formation of carbon deposits are the major known limitations although the specific causes are unidentified. It is proposed that the known limitations could be reduced by selectively reforming specific fractions of the bio-oil. The hydrophobic fraction composed of phenolic and furan derived compounds can be separated by water extraction as a high-value product. In the current work, the particular interest is on efficient hydrogen production from the residual aqueous fractions. There are certain challenges introduced due to the complexity of these mixtures. An improved understanding of the underlying steam reforming characteristics of pyrolysis liquids compounds will provide the opportunity to predict hydrogen yields and to potentially identify undesired compounds. Different fractions were being studied to determine which ones can be used more efficiently to produce hydrogen with existing steam reforming technologies. A fractionating condenser system was used to collect different fractions of fast pyrolysis liquids. The hydrophilic components from the different fractions were analyzed and steam reformed using a nickel-based commercial catalyst loaded fixed bed reactor. The results from these studies are used to correlate the steam reforming efficiency to the characteristics of the fractions. The performance of a combined catalyst-sorbent will also be discussed in comparison to hydrogen yields obtained from bio-oil with the commercial catalyst.