Transparent conductive electrodes, as transmission windows of photons and electrons, play important roles in high‐performance organic optoelectronic devices. The replacement of widely used indium tin oxide (ITO) electrodes has been attempted due to the increasing cost and intrinsically brittle characteristics of ITO. Ultrathin metal films, with excellent optoelectrical features, high flexibility, and sufficient mechanical stability, have been considered a potential candidate for the use as transparent conductive electrodes. However, ultrathin metal films follow the Volmer–Weber mechanism, resulting in a rough and discontinuous morphology with poor optoelectrical properties due to the bad adhesion to substrates. This review summarizes the progress in strategies for preparing ultrathin and ultrasmooth metal films with superior transmittance and conductivity by successfully suppressing the Volmer–Weber mechanism. The electrical and optical performances of the ultrathin metal films based on improved nucleation processes, as well as applications in ITO‐free organic optoelectronic devices, are also described and discussed in detail. The development of ultrathin metal films with improved metal nucleation processes based on various strategies is summarized in this review. The great progress in the properties of ultrathin metal films as well as their application in indium tin oxide (ITO)‐free organic optoelectronic devices as transparent conductive electrodes are described.