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Recent progress in addressing electrically driven single‐molecule behaviors has opened up a path toward the controllable fabrication of molecular devices. Herein, the selective fabrication of single‐molecule junctions is achieved by employing the external electric field. For molecular junctions with methylthio (–SMe), thioacetate (–SAc), amine (–NH2), and pyridyl (–PY), the evolution of their formation probabilities along with the electric field is extracted from the plateau analysis of individual single‐molecule break junction traces. With the increase of the electric field, the SMe‐anchored molecules show a different trend in the formation probability compared to the other molecular junctions, which is consistent with the density functional theory calculations. Furthermore, switching from an SMe‐anchored junction to an SAc‐anchored junction is realized by altering the electric field in a mixed solution. The results in this work provide a new approach to the controllable fabrication and modulation of single‐molecule junctions and other bottom‐up nanodevices at molecular scales.