With the adoption of XANES and XPS, an analysis of occurrence characteristics in the organic sulfur of coking coal in Shanxi Province is conducted, with the choice of model compounds of thiophenic sulfur that matches the structure in the coal for the microwave radiation and water bath heating. Through a comparison of Raman Spectrum, a research is carried out into the action of mechanism of sulfur-bearing structure in the model compounds from what is mentioned above, with Materials Studio in place to construct and optimize the structure of model compounds and the application of the theory of density function to conduct computational simulation of the parameters of molecular configuration of model compounds in the microwave field to analyze the response mechanism of sulfur-bearing structure to the microwave. The outcome has established that thiophene is the main occurrence of organic sulfur in the coking coal. After the microwave radiation, there comes a red shift of the absorption peak of Raman regarding carbon-sulfur bonds and sulfur-sulfur bonds in the model compounds, with a comparatively smaller shift with respect to the model compounds that have a rapid temperature rise. There is almost no shift after the water bath heating under the same temperature. The microwave energy is not powerful enough to break carbon-sulfur bonds and sulfur-sulfur bonds in the model compounds, but with a change in the molecular configuration. It is likely that the sulfur-bearing bonds in the model compounds have a transition state in the microwave field. As a result, the existence of the nonthermal effect in the thiophenic sulfur structure under the microwave.