Biomass-nitrogen conversion during the pyrolysis and gasification of a cane trash in steam was investigated using a fluidised-bed/fixed-bed reactor and a fluidised-bed/tubular reactor. Our results indicate that the thermal cracking of volatile-N is the main route of HCN formation although the thermal cracking of char-N also contributes to the formation of HCN. There are three major routes of NH3 formation: ‘hydrolysis’ of N-containing structures in the solid phase during the primary pyrolysis, thermal cracking and gasification of solid nascent char as well as the thermal cracking and reforming of volatile-N. Under the current experimental conditions, the hydrolysis of HCN does not appear to be an important route of NH3/HNCO formation.