The need for green renewable sources is adamant because of the adverse effects of the increasing use of fossil fuels on our society. Biomass has been considered as a very attractive candidate for green energy carriers, chemicals and materials. The development of cheap and efficient fractionation technology to separate biomass into its main constituents is highly desirable. It enables treatment of each constituent separately, using dedicated conversion technologies to get specific target chemicals. The synergistic combination of aquathermolysis (hot pressurised water treatment) and pyrolysis (thermal degradation in the absence of oxygen) is a promising thermolysis option, integrating fractionation of biomass with production of valuable chemicals. Batch aquathermolysis in an autoclave and subsequent pyrolysis using bubbling fluidised bed reactor technology with beech, poplar, spruce and straw indicate the potential of this hybrid concept to valorise lignocellulosic biomass. Hemicellulose-derived furfural was obtained in yields that ranged from 2 wt% for spruce to 8 wt% for straw. Hydroxymethylfurfural from hemicellulose was obtained in yields from 0.3 wt% for poplar to 3 wt% for spruce. Pyrolysis of the aquathermolised biomass types resulted in 8 wt% (straw) to 11 wt% (spruce) of cellulose-derived levoglucosan. Next to the furfurals and levoglucosan, appreciable amounts of acetic acid were obtained as well from the aquathermolysis step, ranging from 1 wt% for spruce to 5 wt% for straw. To elucidate relations between the chemical changes occurring in the biomass during the integrated process and type and amount of the chemical products formed, a 13C-solid state NMR study has been conducted. Main conclusions are that aquathermolysis results in hemicellulose degradation to lower molecular weight components. Lignin ether bonds are broken, but apart from that, lignin is hardly affected by the aquathermolysis. Cellulose is also retained, although it seems to become more crystalline, probably due to a higher ordering of amorphous cellulose when the samples are cooled down after aquathermolysis. These NMR results are in agreement with thermogravimetric analyses results.