This work addresses a novel microwave-assisted, acid-catalysed, organosolv (EtOH/H2O) system for the selective fractionation of bamboo, examining the effects of the temperature (110-190 degrees C), solvent system (EtOH/H2O) and catalyst amount (0-5 vol.% formic acid) on the process. The statistical analysis of the results revealed that the operating variables have a significant influence on bamboo fractionation, allowing the selective production of (i) a cellulose-rich solid fraction, (ii) a hemicellulose rich water-soluble fraction and (iii) a lignin rich solid fraction. The yields of each of these fractions varied between 51 and 94%, 2 and 23% and 2 and 32%, respectively. Increasing temperature exerted a positive effect on bamboo decomposition, increasing the overall bamboo conversion and influencing the effect that the solvent system (EtOH/H2O) has on the process. At low temperature (110 degrees C) the solvent system does not have much influence, while a synergetic interaction between EtOH and H2O took place at higher temperatures, which allowed better results to be obtained with EtOH/H2O mixtures than with the pure solvents alone. The effect of the catalyst was relatively weak, being greatest when using a high temperature (190 degrees C) and high proportions of water (>85 vol.%) in the solvent system. With respect to the properties of each fraction, the cellulose rich solid fraction was made up of un-reacted cellulose (44-83 wt. %), hemicellulose (0-21 wt.%) and lignin (12-34 wt.%); the water-soluble hemicellulose rich fraction consisted of a mixture of oligomers, sugars, carboxylic acids, ketones and furans; and the solid rich lignin fraction comprised high purity (>95 wt.%) organosolv lignin. The optimisation of the process revealed that by using a temperature of 190 degrees C, a solvent system consisting of 45 vol.% EtOH and 55 vol.% H2O with a concentration of formic acid of 5 vol.% it is possible to fractionate bamboo into a high purity (84 wt.%) cellulose solid fraction, very pure (>95%) organosolv lignin and a rich water-soluble hemicellulose fraction consisting of a mixture of oligomers (27 wt.%), sugars (56 wt.%) and carboxylic acids (14 wt.%); thus converting this process into a very promising method for the selective fractionation of bamboo.