The pyrolysis of rice straw was studied to estimate the effect of pyrolysis conditions on product yields and bio-oil composition when the heating rate was 5 K/min. Pyrolysis temperature, particle size, sweeping gas flow rate and steam velocity were the experimental parameters. Among the four pyrolysis temperatures; namely, 673, 773, 823 and 973 K; 823 K gave the highest bio-oil yield of 27.26%. Six different particle sizes were examined and sample having a particle size of 0.425 < D-p < 0.85 mm had a bio-oil yield of 27.77%. Nitrogen was used as the sweeping gas with the flow rates of either 50, 100, 200 and 400 ml/min and the highest bio-oil yield was obtained when flow rate was 200 ml/min. The bio-oil yield reached a maximum value of 35.86% with the steam velocity of 2.7 cm/s. Liquid products obtained from pyrolysis, inert atmosphere pyrolysis and steam pyrolysis were then fractionated into aspalthanes and maltanes. The aliphatic subfraction obtained by column chromatography was then analysed by GC/MS. For further structural analysis, the pyrolysis oils were conducted with H-1-NMR, oils and aliphatic subfractions with FT-IR. The chemical characterisation has shown that the oil obtained from rice straw may be potentially valuable as fuel and chemicals feedstocks. (C) 2004 Elsevier Ltd. All rights reserved.