In this paper, the poly(acrylonitrile-acrylamide-acrylic acid) [P(AN-AM-AA)]/poly(vinyl alcohol) (PVA) intermacromolecular complex formed through hydrogen bonding is described. The experimental results show that P(AN-AM-AA), which was prepared by hydrolysis of polyacrylonitrile followed by acidifying, complexes with PVA through hydrogen bonding, as verified by pH value testing and FTi.r, thermal analysis demonstrates that the complex formed is superior in thermal stability, compared with its component polymers. Favourable conditions for complexation of P(AN-AM-AA) with PVA are : AA content in P(AN-AM-AA) : 41-46%; a ratio of P(AN-AM-AA) to PVA in the range 1:20-1:10; and a solution pH value of 5.0-5.5.