The flash pyrolysis of polyacrylamide (PAM) in Ar atmosphere was carried out in a tube-type pyrolyzer at 700 A degrees C for 5 min. The volatile products were detected and identified by gas chromatography combined with mass spectrometry (GC/MS). Twenty four kinds of pyrolysis products were identified. In particular, some products, such as acetaldazine and 4-hydroxy-4-methyl-2-pentanone, were the first reported existing in the PAM pyrolysis products, which should play an important role in improving the igniting and combustion performance of Al-H2O-based propellants. Moreover, the flash pyrolysis residues were analyzed by FTIR. The experimental results show that the pyrolysis products of PAM can be roughly divided into five types. The products of five types promote the igniting and combustion performance of Al-H2O-based propellants, and the mechanisms of formation of every type are discussed.