This article is concerned with the microstructural changes during peroxide and high pressure vulcanization of polybutadiene that is unfilled and filled with carbon black. The main tool is C-13 solid-state NMR; it shows that vinyl unsaturations are consumed in both filled and unfilled samples under peroxide and high pressure vulcanization. Chemical shift calculations of unvulcanized polybutadiene show good agreement with the observed peaks. Calculations of proposed structures, based on a possible reaction mechanism, suggest that a large number of peaks will appear, each at very low intensity. Nevertheless, some changes can be seen as a result of the crosslinking reaction, and the results provide support for the suggested reaction mechanism. Thus, the proposed addition crosslinking mechanism over vinyl unsaturations seems to be a reasonable explanation of the crosslink formation in high pressure vulcanization.