We use a scanning tunneling microscope-based break-junction technique to compare the probability of the formation of a single-molecule junction for a series of amine-terminated oligophenyl and alkane species using either Ag or Au as electrodes. For all molecules, we find that there is a significantly higher probability of junction formation when using Ag electrodes than with Au electrodes. We also find that longer molecules have a higher probability than shorter molecules to form a junction for both Ag and Au electrodes. For all molecules, the measured molecular junction length that is formed with the Ag electrodes was longer than that formed with Au electrodes. Furthermore, we can make a single atomic oxygen junction and can measure its conductance using Ag electrodes. These observations are attributed to a narrower gap of the Ag electrodes compared to that of the Au electrodes after the metal contact ruptures. Since there is a high probability of a molecular junction forming when using Ag electrodes, we can therefore perform a statistical analysis within the context of the material properties that are suitable for future molecular electronics. (C) 2014 Elsevier B.V. All rights reserved.