Polybutadiyne samples were heated at 20 degrees C/min up to 1200 degrees C in a pyroprobe attached to a gas chromatograph/mass spectrometer (GC/MS). Analysis of the volatiles evolved during heating identified carbon dioxide (adsorbed on polymer surface), methane, ethylene, benzene, toluene, and traces of higher aromatics. Correlations have been made between sample temperature and evolution (onset, maximum, and end temperatures) of each of the five listed volatiles. Average polybutadiyne weight loss at 1200 degrees C was 14 +/- 2%. Two cure studies were performed in the pyroprobe, and it was shown that both weight loss and volatile evolution were affected. The results were consistent with a higher degree of polymer crosslinking as cure time and temperature increased.