The molecular structure of coal is complex, and the existing research methods are limited, so it is difficult to clarify its influence mechanism on the spontaneous-combustion characteristics of coal. In this paper, the previous extraction, FTIR, TPR, TG-DSC and other experimental results are combined to analyze the extraction weakening effect and the correlation analysis of the spontaneous-combustion characteristic parameters of raffinate coal. The results show that extraction can destroy the connection bond of coal molecules, change the content of dominant active groups in the coal spontaneous-combustion reaction, increase the lower limit of the key temperature nodes of coal spontaneous-combustion or extend the temperature range, resulting in an increase in the ignition-point temperature of coal and a decrease in coal quality. This paper will provide a theoretical basis for the study of the microscopic mechanism of coal spontaneous-combustion and then provide new ideas for the development of an active prevention and control technology for coal spontaneous-combustion.