A perovskite type superconductor film having a high content, almost a single phase, of the high Tc phase is formed by the steps of: depositing at least one first film of a first material (e.g., a composite oxide of Bi-Sr-Ca-Cu-O system or Tl-Ba-Ca-Cu-O system) constituting a perovskite type superconductor over a substrate; depositing at least one second film of a second material containing an oxide or element (Bi.sub.2 O.sub.3, Tl.sub.2 O.sub.3, PbO.sub.x, etc., particularly PbO.sub.x) having a vapor pressure of more than 10.sup.-4 Pa at 800.degree. C. at least as a main component over the substrate; to thereby form a stack of the first and second films; and heat treating the stack of the first and second films to form the perovskite type superconductor film on the substrate. Further, preferred compositions of the as-deposited films or stack are determined.