W(15 Å)/C(15 Å), W(50 Å)/C(50 Å) and W(100 Å)/C(100 Å) periodic multilaver films were prepared by magnetron sputtering and suhsequently annealed at 980, 730 and 500°C. The changes of layered and crystal structures were studied by x-ray diffraction. The results depended largely on the thickness of W layers and their initial crystal struictures of W. The kinds of transformations are classified into two types: one is the non-reacting type in the case of multilayers having the thinner W layers like W(15 Å)/C(15 Å), in which the crystallization of W layers prevails over the reactions between W and C layers; the other, the reacting type in the multilayers having thicker W layers like W(50 Å)/C(50 Å) and W(100 Å)/C(100 Å), in which reactions Prevail over crystallization. A tentative model in which the effective reaction rate between amorphous–W and amornhous–C is much smaller than that of crystalline-W(beta phase) and amorphous-C is proposed to explain the origin of the phenomena.