Tectonic coals, formed under the action of tectonic stress, easily deformed and broken up, were found in many countries that produce coals. Tectonic deformation changes the macromolecular structure and the chemical compositions of coals in a certain degree, and at the same time it can influence deeply the nano-scale pore structure of tectonic coals (<100 nm). It is the main adsorption space of coalbed methane. By means of measurement of the maceral compositions and reflectance of vitrinite, systematic researches were performed on the classification system of nano-scale pores structure suitable for tectonic coals and the structural evolution of nano-scale pores of fifteen sets of tectonic coal samples which belong to different deformation series formed by three metamorphic and deformed environments from 11 coal mines and theirs formation mechanism in the Huaibei-Huainan mine area, southern North China. Using the low-temperature nitrogen adsorption method, the images of coal macromolecular pore structure obtained in the high-resolution transmission electron microscope show a natural classification system of nano-scale pore structure of different kinds of tectonic coals. In Accordance with the pore diameter, there are four types, mesopores (15~100 nm), micropores (5~15 nm), sub-micropores (2.5~5 nm), and ultra-micropores <2.5 nm). In metamorphic and deformation environments of low-rank coal, as the deformation becomes stronger, the volume of mesopores of tectonic coals reduces rapidly, while the volume of micropores and pore diameter lower than micropore increase obviously, and sub-micropores and ultra-micropores can be found, and the specific surface area of mesopores reduces rapidly and the amount of micropores and sub-micropores increase. From brittle coal to ductile deformation coal, the parameters such as total volume of pores, the pore specific surface area (include BET method and BJH method) and the adsorption of nitrogen change with the deformation. If the deformation becomes more intense, these parameters will increase rapidly, and at the same time the medium semi-diameter reduces further. Inhomogeneous coal has a similar change of pore parameter as weak brittle deformation coal. In metamorphic and deformation environments of the middle- and high-rank coal, tectonic coals have a similar parameter changing with low-rank coal. But, there are differences in pore structural evolution of tectonic coals formed in different metamorphic and deformation environments. In short, the increase of temperature has not much influence on the structure of nano-scale pores, while structural stress has an important influence on the parameters of pore structure of tectonic coals. Under the thermal condition, orientation of structural units appears in certain parts, the pore structure are mainly micropore and sub-micropores, and the ultra-micropores are also exist, but the connection becomes worse. In the local orientation process of aromatic structure units, special thin-neck-bottle-shaped pores developed, and the pores are mainly built up by pores between the oriented and un-oriented units.