The primary tars obtained by the Fischer-Schraeder method fr om coals described in earlier papers [1] were studied using infrared (i.r.) and H-1 nuclear magnetic resonance (nmr) spectroscopy methods. With the object of achieving a broader evaluation of the properties and structure of these primary tars with increase in coalification of the parent coals-from 78 to 86% C-daf, in the range from gasflame (according to Polish classification) 611-VII (according to international classification and statistical groups) to orthocoking 435-VB coals-they were distilled to the temperature of 543 K under normal pressure. Products obtained were also analysed by the i.r. and H-1 nmr spectroscopy methods, while the distillates/fraction boiling up to 543 K/were additionally analysed by the pas chromatography-mass spectrometry (g.c.-m.s.) and C-13 nmr methods. A comparative X-ray analysis of the coals and the semi-cokes obtained from them was also conducted.