Coking coal is an important raw material for coke production. In this study, in an inert atmosphere, two Chinese coking coal samples were, respectively, heated gradually to 1200 °C to release volatile and form char and coke in succession, then cooled naturally to close room temperature to age the coke. The whole heating and cooling process on carbonization were monitored in situ by simultaneous small and wide-angle X-ray scattering (SAXS-WAXS) technique based on a synchrotron radiation platform. The simultaneous structural changes of pore and skeleton in coal during carbonization are revealed for the first time. The two raw coal samples, with similar carbon content and slightly different coalification degree, undergone a carbonization process similar in whole and different in parts. The carbonization presents approximately three stages during heating process and one stage during cooling process. The coal structure changes wavily during heating and monotonously during cooling. The corresponding structural change mechanism is analyzed.