One-dimensional nanostructures, with a high ratio of surface-bulk atoms, find applications as active catalysts. Here, we report tunability in ultrathin single-crystalline AuPdPt nanowires by modifying synthesis conditions and postsynthetic treatment in a controlled ambient atmosphere. The surface microstructure modification of these nanostructures has been analyzed by integrating the results of three crucial techniques including Z-contrast HAADF-STEM imaging, X-ray photoelectron spectroscopy, and electrochemically active surface area from cyclic voltammograms.