Aqueous phase of bio-oil (APB) is a general stream of waste produced from biomass pyrolysis and fractional condensation of pyrolytic volatiles and has very limited applications. We have demonstrated a sequence of leaching of alkali and alkaline earth metallic species (AAEMs) from char and catalytic hydrothermal gasification (CHTG) for valorizing char and APB, respectively. The majority of AAEMs can be removed from the char by leaching with APB and the removal rates were almost equivalent to those leached with HCl (1.0 M). CHTG of an aqueous solution of the spent APB with a total organic carbon of 14,450 ppm was performed in a continuous flow reactor, employing an activated carbon-supported Ru catalyst (Ru loading, 4.6 wt%). The catalyst exhibited a stable activity for carbon conversion of 98.8 % at 350 °C for at least 360 min while gaseous product consisting of H2, CH4, and CO2 was produced with a cold gas efficiency of 101–103 %, on a higher heating value basis. The cold gas efficiency exceeding 100 % is mainly because of the generation of H2 from water through water-gas shift reaction. The CHTG performance of APB was enhanced by char leaching through the uptake of coke-forming precursors of APB onto char and the enrichment of AAEMs in the spent APB. These AAEMs played roles in suppressing coke formation and deposition onto the catalyst and maintaining Ru particle size by providing a less acidic hydrothermal environment.