Scanning tunneling microscopy (STM) has gradually matured into a powerful tool for imaging electrode surfaces in the electrochemical environment with atomic resolution. It has been used to elucidate numerous old puzzling structural issues and to reveal many new interesting phenomena. As an imaging tool, it will continue to contribute to the understanding of various electrochemical processes on electrode surfaces. STM is more than an imaging tool for structural characterizations, other important electrochemical applications, such as probing electron transfer processes, fabricating nanostructures and studying fast electrochemical kinetics, have also been actively pursued. These later unconventional applications are the focus of this discussion.