Biomass fractionation is performed with a modified Clextral twin-screw extruder used as a thermo-mechano-chemical reactor. This new process is firstly analyzed. Visual observations, residence time distributions, and global mass balances are used to obtain information about the process phenomena and their coupling. Residence time distributions (RTD) classical models are adopted to represent the experimental plots. The influence of continuous and discrete process parameters upon the RTD of the solid and liquid phases is analyzed.