Direct analysis in real time (DART) ionization technique coupled with a quadrupole time-of-flight mass spectrometry (Q-TOF MS) with high resolving power was applied to characterize raw coal and coal derivatives in the solid state. Desorption and ionization under optimized parameters allowed for the detection of small molecules scattered inside pores of a macromolecular network of raw coal. Use of the second-stage MS (Q-TOF) significantly contributed to the structural elucidation of compounds in coal and coal derivatives.