We have proposed that solid-state reaction (SSR) of compositionally modulated thin multi-layered filins. can be one of the profitable structural control techniques for synthesizing novel nano-structured thin film materials. This is because the SSR process should not only be dominated by total composition of multilayered filins, but also by local composition at the interfaccs of the multilayers, through the nucleation and growth process of reacted compounds. In this paper, we discuss a phase prediction method by SSR of multilayered films based on the modified effective heat of formation rule. In addition, some experimental results oil the fabrication process of nano-structured films by the SSR technique are also described. (C) 2002 Elsevier Science B.V. All rights reserved.