Vitrinite is the maceral which has regularly changing property with coal structure, and it is also a main component affecting the coal quality. A high resolution TEM (HRTEM) with point resolution of 2.1 A was used to analyze the macromolecular structure of some coals of different ranks. Nonhomogeneous pore structure of anthracite macromolecules can be directly characterized by HRTEM. The degree of molecular orientation of Jingxi anthracite is stronger than that of Jincheng anthracite. The former is mainly composed of parallel aromatic stack and pre-oriented structures, while the latter granular structure. HRTEM technique is an effective method used for coal molecular structure and coalification nature studies.