A roll of a web composed of an aromatic polyimide composite film and a metal film in which the polyimide composite film is composed of a non-thermoplastic aromatic polyimide base film and a thermoplastic aromatic polyimide cover film, the polyimide composite film showing a heat shrinkage ratio of less than 0.1% at 300° C., can be produced by heating a corresponding roll of web composed of a metal film and an aromatic polyimide composite film having a heat shrinkage ratio of more than 0.1% at 300° C., at a temperature between 150° C. and a glass transition temperature of the thermoplastic aromatic polyimide cover film, for a period of at least one minute.