As a renewal energy source for bioethanol production, the residuum of apple wood likely offers a major benefit by having the lignin portion transformed into biofuels firstly. In this study, we used the residuum of Raney Ni and Ru/C catalyzed and hydro-deoxygenated (for jet-fuel production) apple wood as the start substrate to produce bio-ethanol. Cellulose content could reach 83.38% for residuum of Ni catalyzed substrates (Ni-cs for short), and the enzymatic hydrolysis rate increased to 88% which is in reasonable high scale. Lignin left in residuum showed more negative effect on cellulose enzymatic hydrolysis than cellulose II. Different catalysts (Ni or Ru/C) concentration influenced the enzymatic hydrolysis and fermentation. Using quasi-simultaneous enzymatic saccharification and combined fermentation (Q-SScombF), the inhibit effect from catalysts was obvious and the ethanol production efficiency were lower than 35%. But for separate hydrolysis and fermentation process (SHF), the ethanol conversion of raw material and catalyzed residuum improved from 33% to 75% (for residuum of Ni-cs) and increased from 25% to 73% for residuum of Ru/C catalyzed substrates (Ru/C-cs). This research provided a good basis for the feasibility of bio-ethanol production from residuum of bio-refined apple wood.