Biological treatments of Residual Municipal Solid Waste (RMSW) allow to divert biodegradable materials from landfilling and recover valuable alternative resources. The biodegradability of the waste components needs however to be assessed in order to design the bioprocesses properly. The present study investigated complementary approaches to aerobic and anaerobic biotests for a more rapid evaluation. A representative sample of residual MSW was collected from a Mechanical Biological Treatment (MBT) plant and sorted out into 13 fractions according to the French standard procedure MODECOM™. The different fractions were analyzed for organic matter content, leaching behavior, contents in biochemical constituents (determined by Van Soest's acid detergent fiber method), Biochemical Oxygen Demand (BOD) and Bio-Methane Potential (BMP). Experimental data were statistically treated by Principal Components Analysis (PCA). Cumulative oxygen consumption from BOD tests and cumulative methane production from BMP tests were found to be positively correlated in all waste fractions. No correlation was observed between the results from BOD or BMP bioassays and the contents in cellulose-like, hemicelluloses-like or labile organic compounds. No correlation was observed either with the results from leaching tests (Soluble COD). The contents in lignin-like compounds, evaluated as the non-extracted RES fraction in Van Soest's method, was found however to impact negatively the biodegradability assessed by BOD or BMP tests. Since cellulose, hemicelluloses and lignin are the polymers responsible for the structuration of lignocellulosic complexes, it was concluded that the structural organization of the organic matter in the different waste fractions was more determinant on biodegradability than the respective contents in individual biopolymers.