Supercritical water gasification (SCWG) of nitriles was studied in a tubular flow reactor at different temperatures. This article focuses on the product distributions and corresponding reaction pathways influenced by addition of Na(2)CO(3) catalyst. Results showed that gas yield for both acetonitrile and acrylonitrile can be greatly enhanced by adding Na(2)CO(3) catalyst. Especially, H(2) gasification efficiency can reach 55.4% and 123.3% at 550 degrees C, respectively. But the catalytic effect on the gas yield of benzonitrile was relatively insignificant. Na(2)CO(3) can also accelerate the hydrolysis of cyanogen and amido as a base catalyst. Benzene and acetic acid were the primary intermediate products during the SCWG of benzonitrile and acetonitrile, respectively. The conversion of acrylonitrile was more complicated because of the activity of double bond. It is possible that 3,3' iminodipropionitrile was formed by Na(2)CO(3) catalyzed in the range of 490-520 degrees C, which dominated two thirds of pathways for the subsequent formation of acetic acid. Ammonia-nitrogen content in the liquid effluent was limited by the hydrolysis degree of cyano-group and the possible polymerization reaction of intermediate products. There was no obvious trend to reveal that NH(3) was converted into nitrogen under our experimental conditions. (C) 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.