Integrated studies of green coke have been carried out by means of X-ray diffractometry, electron microscopy, electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR). It is determined by EPR spectroscopy that two types of radical structures are present in the samples: low-molecular aromatic radicals and conjugated polyaromatic structures in which the unpaired electron is delocalised. Analysis of line shapes in the EPR spectra reveals differences between the green coke samples under investigation. EPR is shown to be highly sensitive method allowing one to follow the changes of molecular structure during the production of green coke. The results obtained in the work with the help of EPR are in good agreement with the results of NMR spectroscopic studies. It is concluded that evaluation of the molecular structure of intermediate coking products is necessary to improve the composition of initial raw material and technological operations.