An 81 day trial compared the cumulative production of methane from rape straw pre-treated by steam explosion at 15 levels of severity. The final methane yields were similar. The temporal variation in production rate exhibited two peaks: maximum production occurred in the first peak at around 21 days with heights that increased with severity; the height of the second peak reduced with severity and peaked between 32 and 36 days. Changes in the straw composition were investigated using mid-infrared spectroscopy. These were also strongly related to the degree of severity, allowing good predictive models to be built of severity and subsequently the rate of methane production. The main spectral changes showed the degradation of cellulose and xylose-containing hemicelluloses and production of furfural-like components commonly associated with biomass pre-treatments. Only small changes to lignin were associated with increased methane generation suggesting a structural rather than chemical role in this process. (C) 2012 Elsevier Ltd. All rights reserved.