Lignocellulosic biomass is a renewable feedstock that has the potential to replace the diminishing fossil fuels. Herein, we reported the simultaneous conversion of cellulose, hemicellulose and lignin from raw biomass into gasoline alkanes (hexanes and pentanes) and monophenols and related hydrocarbons over layered LiTaMoO<inf>6</inf> and Ru/C in aqueous phosphoric acid medium. Specifically, gasoline alkanes were directly yielded from the carbohydrate components, based on hemicellulose and cellulose, and the total yield could be up to 82.4%. Notably, the lignin fraction could also be transformed into monophenols, related alcohols and hydrocarbons by the one-pot reaction. It suggested that the hydrocracking of monophenol fraction could be performed in this catalytic system. The total yield of volatile products was 53% based on the lignin fraction. In this paper, the influences of phosphoric acid concentration, substrate ash and the amino acids derived from the biogenic impurities were investigated and different raw biomass substrates were tested. Furthermore, the catalysts could be reused for several runs to convert raw biomass without pretreatment.