Simple and efficient catalytic routes have been explored to upgrade the raw lignin oil. Though homogeneous catalysis is easy to operate and possesses a high reaction rate, it also suffers from the difficulty of product separation. In this work, we used H3BO3 as a novel homogeneous catalyst coupled with Ru/C to overcome the separation problem and carry out the hydrodeoxygenation (HDO) of phenolic compounds and raw lignin oil. H3BO3 showed an outstanding performance over the liquid organic and mineral acids, with a good catalyst recyclability. Phenolic model compounds including monomers and dimers can be efficiently converted into cycloalkanes with yields close to 100%. Moreover, the raw lignin oil also had a good HDO result by using this bifunctional catalyst (H3BO3 and Ru/C). The content of hydrocarbons increased from 7.9% to 93.1% at 260 degrees C, which promoted the upgraded lignin oil capable to be used as fuel directly.