In a diluted sulfuric acid/toluene system with an extremely low water/solid ratio (short in the ELW system), hemicellulose from corncob is quickly converted to furfural with high yields (> 60 mol%). In order to establish an economic and effective biorefinery system, further research about the use of ELW residues is needed. Through the composition analysis, FTIR analysis and Raman analysis, it was found that the weak carbonization characteristics of ELW residue, and the hydrocarbonization mechanism was explained based on the thin acidic aqueous film hypothesis. Taking the furfural plant hydrolysis residue (short in FP residue) as a control, this research comprehensively compared the potential of ELW residue and plant residue as solid fuels for combustion, pyrolysis (conventional pyrolysis and rapid pyrolysis) and high value utilization. In conclusion, the high calorific value and conventional pyrolysis products of ELW residue were similar to FP residue; but the yield of levoglucosan from ELW residue was 2.53 times higher than that of FP residue, which was 51.78% and 20.43% of theoretical yield, respectively. This paper shows a comprehensive biorefinery system combined with an advanced technology for furfural production (ELW system) and an effective thermochemical means to achieve the maximum utilization efficiency of resources.