Corn kernels are good candidates for production of various value-added products such as gas biofuel, hydrogen due to the carbohydrate-rich composition. In this study, widely grown corn, field corn kernels were dissolved in subcritical water at different temperatures to determine optimal thermal hydrolysis condition. Organic-rich hydrolysate obtained from hydrolysis process was gasified by aqueous-phase reforming (APR) for hydrogen gas production. Since hydrolysis at 200 °C resulted in significantly more total organic carbon release than other temperatures and the lowest amount of insolubilized solid residue. Different concentrations of this hydrolysate (diluted with water at different ratios) were evaluated for high yielding hydrogen gas production. Gasification performance of corn kernels was also compared with lignocellulosic biomass using corn stover as a representative biomass material. The hydrolysate with 2486 mg/L TOC concentration showed the best performance for hydrogen gas production (130 mL H2/g corn) and left less amount of ungasified solid residue. Corn kernels produced 2.3 times more hydrogen gas compared to corn stover biomass. Thus, corn kernels are promising feed materials for APR process, and excess production of corn can be utilized for hydrogen gas production in higher yield and richer composition.