Ethyl vanillate (EV) is an important component of flavors and fragrances and has been widely used in the food, pharmaceutical, and cosmetic industries. The highly selective preparation of EV from lignin, the most abundant monophenolic compound in nature, is a great challenge in the field of lignin depolymerization. In this study, the multi-active catalysts from alkaline ionic liquid and polyoxometalates were constructed, which were characterized by acidity, alkaline and oxidizing ability. They can efficiently cleave the CC and CO bonds of larch lignin in an ethanol/water system at 160 °C for 10 h with H