Polyvinylamine (PVAm) and polyvinylamine chloride (PVAm•HCl) were synthesized by Hofmann degradation of polyacrylamide (PAM). The reaction condition is gentle and the operation is safe, simple and economical so that it is a good reaction method. The chemical structures and thermal properties of the polymers were studied by Fourier transform infrared spectrometer (FTIR), nuclear magnetic resonance spectrometer (NMR), X-ray diffractmeter (XRD) and thermogravimetric analyzer (TGA). Synthesis of PVAm•HCl was confirmed by the intensities of the characteristic peak of -CONH2 decreased and the appearance of a new absorption peak at 1530cm-1 (due to N-H bond of -NH3+ ) in the FTIR spectrum, the appearance of the characteristic absorption peaks of carbon atoms in the 13C NMR spectrum, the appearance of chemical shift assignments of proton in 1H NMR spectrum and the appearance of characteristic dispersing diffraction peak between 22.5° to 25.2° in the XRD spectrum, respectively. PAM had three decomposing stages, but PVAm•HCl had two decomposing stages. TG curve of PAM and PVAm•HCl showed that the initial decomposition temperature were 190oC and 140oC, respectively. The thermal stability of PVAm•HCl was poorer than that of PAM.