The removal of tar and lower hydrocarbons is a vital technological barrier hindering the development of biomass gasification. The present work evaluates four olivine catalysts (three untreated of different origin and one calcined) for lowering the amount of these compounds in biomass derived syngas by reforming model compounds (naphthalene, toluene, and methane). Treatments prior to reaction were shown to largely impact the catalytic activity and physiochemical properties of the olivine catalysts depending on its origin. The formation of free Fe phases following decomposition of a Fe-bearing serpentine phase ((Mg,Fe)(3)Si2O5(OH)(4)) near the surface of untreated olivine catalysts proved most important for facilitating higher activity compared to olivine catalysts with little or no serpentine phase initially. The most active catalyst was efficient at naphthalene removal (90% conversion at 800 degrees C), but more active catalysts are needed for applications where methane removal is required. Additionally, carbon deposition during naphthalene-steam reforming as well as Fe clustering during naphthalene-steam reforming and exposure to reducing conditions suggested stability may be a liability. (C) 2007 Elsevier B.V. All rights reserved.