The dynamics of carbon (C) and nitrogen (N) of plant residues and organic fertilisers are of great interest for agricultural and global warming studies. The proportion of the fractions obtained from biochemical analyses (fibres by sequential Van Soest analysis) can be used for predicting both C and N transformation of organic materials in soils. Considering the expensive and time-consuming Van Soest method, the principal aim of this study was to elaborate near infrared (NIR) calibrations for fibres, in order to use them for consecutive studies (for example, our works on transformation of added organics or TAO model). A wide set of organic fertilisers and their raw materials was sampled, including plant materials originating from temperate (especially Mediterranean) and tropical regions. The particular objective of this work was to build NIR calibrations for fibre fractions, along with C and N content, in plant materials used in the organic fertiliser industry and green house gases mitigating strategies. The second particular objective was to test for two levels of validation of the equations previously elaborated: (1) validation with a set of randomly chosen samples that was not considered during the calibration step, (2) extrapolation of the predictive capacity of the equations when applying them to outliers that were previously discarded. The fibres were the best predicted parameters, as R² = 0.95, 0.91, 0.97, 0.97 for neutral detergent soluble, hemicelluloses, cellulose and lignin, respectively, whereas the characteristics of total organic matter had R² varying from 0.87 (N Kjeldahl) to 0.94 (C Dumas). The accuracy of the calibrations developed for fibres was confirmed by the first level of validation, since the standard errors of prediction were close to the corresponding standard errors of cross-validation and the standard errors of calibration. Nevertheless, the calibrations developed for ash and C Dumas were not so good. Surprisingly, at the second level of validation, some outliers were not so badly predicted. This can illustrate the robustness of the calibrations for cellulose, lignin and, to a lesser extent, N Dumas which are key parameters for our modelling works on C and N transformation of added organics in soils.