Superconducting BiPbSrCaCuO thin films were prepared on MgO(001) and Ag/MgO substrates using an electron beam (e‐beam) evaporation technique. The effects of annealing temperature and Ag diffusion on the crystalline structure and some superconducting properties, respectively, were investigated by X‐ray diffraction, atomic force microscopy, and by measurements of the critical temperature and the critical current density. It was shown that an annealing of both types of films at 845 or 860 °C resulted in the formation of mixed Bi‐2223 and Bi‐2212 phases with a high degree of preferential orientation with the c‐axis perpendicular to the substrates. The slight increase of the critical temperature from 103 K to 105 K, the enhancement of the critical current density from 2 × 103 to 6 × 104 A/cm2, and the improved surface smoothness are due to a possible silver doping from the substrate.