Abstract: The acid pickling and demineralization for vitrain samples of fat coal, coking coal, lean coal and meager coal from 8^# coal seam of Taiyuan Xishan, China was accomplished. Meanwhile, both the trace elements testing and curve fitting of infrared spectra of the samples were carried out. It shows that correlation between some of organic group and trace elements in vitrain may be positive changes, or negative changes, or they suddenly be positive or negative with the deepening of coal metamorphism. Accordingly, organic structure-groups in coal can be divided into three types: affinity organic groups for trace elements, abhorred organic groups for trace elements and the neutral organic groups which neither affinity nor abhorred for trace elements. It is discovered that the mutual selection is very intense between organic groups and trace elements in vitrain. Whether typical affinity organic groups or typical abhorred one for trace elements, their change of affinity or abhorred are all abide by a common law, namely, the element periodic law. Even if neutral ones, its tendency of affinity or abhorred for lithophile element, chalcophile and siderophile elements are obviously different.