Solid fuels represent one of the most used sources of energy in many countries. In terms of ranking for the coal deposits, Romania occupies the 26th place in the world, and the 11th place in Europe, with reserves of 22 million tones of bituminous coal (BC) and 472 million tones of lignite. The National Bituminous Coal Company extracts the most significant amount of BC from the Jiu Valley area, a Subcharpatian basin in the Parâng Mountains. In the present article, the BC extracted from the Livezeni depth mine next to Petroşani city is investigated from the microstructural, thermal, and kinetic point of view, in comparison with a sample from Ural Mountains in Russia. Scanning electron microscopy, FTIR spectroscopy, and thermal analysis (TG/DSC/DTA in air and inert atmosphere) measurements were performed. The KAS isoconversional kinetic method was applied for the in-depth understanding of thermal decompositions and burning processes that occur. Even if the thermal behavior of the two samples is generally similar, the non-isothermal kinetic study revealed important differences in the pathways of the oxidative decomposition of volatiles and formation of coke. Also, the kinetics of coke burning depends only on the amount of fix carbon, regardless of the provenience of BC.