Many oxygen compounds were contained in bio-oil, such as acids, alcohols, ketones, aldehydes, phenols, and sugar. Acetic acid, ethylene glycol, butanone, furfural, and m-cresol were selected as bio-oil model compounds in this article. Hydrogen production was carried out via catalytic steam reforming under the conditions of the mole ratio of steam and carbon = 6, liquid hourly space velocity = 5 h(1), and 600 degrees C with catalyst Ni/MgO. Infrared gas analyzer was used to analyze gas concentration via catalytic steam reforming of model compounds on line, while the liquid products from a collection device were analyzed by gas chromatography/mass spectrum. Intermediates were formed under catalytic steam reforming through elimination and recombination reaction, etc. The intermediates reacted with steam to produce H-2 and CO2, and then the reactions reached equilibrium in the end. The hydrogen yield of acetic acid, ethylene glycol, and butanone as materials were higher than that of furfural and m-cresol as materials at the same conditions. The lowest hydrogen yield is only 34.0% (m-cresol as feedstock) and the highest hydrogen yield is up to 78.6% (butanone as feedstock).