The C mineralisation pattern during the early stage of decomposition of plant materials is largely determined by their content of different carbohydrates. This study investigated whether detailed plant analysis could provide a better prediction of C mineralisation during decomposition than proximate analysis [neutral detergent solution (NDF)/acid detergent solution (ADF)]. The detailed analysis included sugars, fructans, starch, pectin, cellulose, lignin and organic N. To determine whether differences in decomposition rate were related to differences in hemicellulose composition, the analysis particularly emphasised the concentrations of arabinose and xylose in hemicelluloses. Carbon dioxide evolution was monitored hourly in soil amended with ten different plant materials. Principal component and regression analysis showed that C mineralisation during day 1 was closely related to free sugars, fructans and soluble organic N components (R 2 = 0.83). The sum of non-cellulose structural carbohydrates (intermediate NDF/ADF fraction) was not related to C mineralisation between days 1 and 9. In contrast, a model including starch and protein in addition to the non-cellulose structural carbohydrates, with the hemicelluloses replaced by arabinose and xylose, showed a strong relationship with evolved CO 2 (R 2 =0.87). Carbon mineralisation between days 9 and 34 was better explained by xylan, cellulose and lignin (R 2 =0.72) than by lignocellulose in the ADF fraction. Our results indicated that proximate analyses were not sufficient to explain differences in decomposition. To predict C mineralisation from the range of plant materials studied, we propose a minimum set of analyses comprising total N, free sugars, starch, arabinose, xylan, cellulose and lignin.