The work was conducted to investigate pyrolysis characteristics and kinetics of low rank coals relating with coal structure by thermogravimetric analysis (TGA), the distributed activation energy model (DAEM) and solid-state C-13 Nuclear Magnetic Resonance (NMR). Four low rank coals selected from different mines in China were studied in the paper. TGA was carried out with a non-isothermal temperature program in N-2 at the heating rate of 5, 10, 20 and 30 degrees C/min to estimate pyrolysis processes of coal samples. The results showed that corresponding characteristic temperatures and the maximum mass loss rates increased as heating rate increased. Pyrolysis kinetics parameters were investigated by the DAEM using Miura integral method. The DAEM was accurate verified by the good fit between the experimental and calculated curves of conversion degree x at the selected heating rates and relatively higher heating rates. The average activation energy was 331 kJ/mol (coal NM), 298 kJ/mol (coal NX), 302 kJ/mol (coal HLJ) and 196 kJ/mol (coal SD), respectively. The curve-fitting analysis of C-13 NMR spectra was performed to characterize chemical structures of low rank coals. The results showed that various types of carbon functional groups with different relative contents existed in coal structure. The work indicated that pyrolysis characteristics and kinetics of low rank coals were closely associated with their chemical structures. (C) 2016 Elsevier Ltd. All rights reserved.