A system of a syndiotactic polystyrene (s-PS)-carbonaceous material, obtained as a result of syndiotactic polymerisation of styrene in the presence of carbonaceous materials of organic origin of different degree of coalification before and after their ammoxidation, was studied. The initial materials were plum stone waste, brown coal and hard coal. The interactions between the system components were studied by the method of differential scanning calorimetry (DSC). It has been found that the type of the carbonaceous material used determines the thermal effects of the phase transitions in s-PS (detected on thermograms) and the melting point of s-PS. It has been shown that on melting of the syndiotactic polystyrene in the presence of the carbonaceous materials containing a relatively large number of oxide groups, the polymer oxidation reactions occur. This effect does not occur when carbonaceous materials with preliminary ammoxidation are applied. (c) 2006 Elsevier B.V. All rights reserved.