Super-critical water gasification of biomass is a promising technology for hydrogen production. In order to achieve high hydrogen yield and complete gasification, the operating parameters were investigated and the solid residual was analyzed to study the reaction bottleneck by Fourier transform infrared spectroscopy and scanning electron microscopy. The experimental results showed that most organic functional groups in corn cob were consumed by super-critical water above 500°C, however, the aromatic substance and cyclic ketone were remained. The K2CO3 has the best catalytic effect due to the formation of pore structure in the residual particle surface. The carbon gasification efficiency of 97.97% and the hydrogen yield was 50.28 mol/kg.