The structural and compositive evolution of tectonically deformed coals (TDCs) and their influencing factors were investigated and analyzed in detail through Fourier transform infrared spectroscopy (FTIR) and laser Raman spectra analysis. The TDC samples (0.7% < Ro,max <3.1%) were collected from Huaibei coalfield with different deformation mechanisms and intensity. The FTIR of TDCs shows that the metamorphism and the deformation affect the degradation and polycondensation process of macromolecular structure to different degree. The Raman spectra analysis indicates that secondary structure defects can be produced mainly by structural deformation, also the metamorphism influences the secondary structure defects and aromatic structure. Through comprehensive analysis, it was discussed that the ductile deformation could change to strain energy through the increase and accumulation of dislocation in molecular structure units of TDC, and it could make an obvious influence on degradation and polycondensation. While the brittle deformation could change to frictional heat energy and promote the metamorphism and degradation of TDC structure, but has less effect on polycondensation. Furthermore, degradation is the main reason for affecting the structural evolution of coal in lower metamorphic stage, and polycondensation is the most important controlling factor in higher metamorphic stage. Under metamorphism and deformation, the small molecules which break and fall off from the macromolecular tructure of TDC are preferentially replenished and embedded into the secondary structure defects or the residual aromatic rings were formed into aromatic structure by polycondensation. This process improved the stability of coal structure. It is easier for ductile deformation of coal to induce the secondary structure defects than brittle deformation.