Coke strength was increased by adding ash-free coal (AFC) binder. In this study, the effect of the AFC binder on the physical and chemical properties of coke was experimentally investigated to understand the molecular mechanism for the improved coke strength. For reduced CO2 emission in steelmaking industry, torrefied biomass fuel mixed with coal binder is also considered. The interface between the base coal and AFC was thus examined using Scanning Electron Microscope (SEM). The coke strength was commonly measured by performing the indirect tensile test and Nuclear Magnetic Resonance (NMR) spectroscopy in 1H and 13C modes. For comprehensive mechanism study of the enhanced coke strength thus obtained, ordinary coal for thermal power plant use was carbonized with AFC for subsequent SEM examination. The NMR spectroscopy results of coke samples positively revealed that the tensile strength was proportional to the average number of aromatic rings.