Abstract: Along the forefront of fundamental research lies the experimental approach toward understanding the behavior of matter at increasingly smaller dimensions. Atomic and molecular scale studies have seen dramatically increased attention over the last twenty years with the invention of scanning probe microscopy (SPM). Future applications of nanoscience to technology critically depend on an understanding of fundamental physiochemical and electronic properties in addition to the development of methods and instrumentation that exploit them. In order to probe chemical systems with spatial resolution on the nanometer scale through imaging and spectroscopy, scanning probe microscopy is a powerful experimental tool. Scanning tunneling microscopy (STM) provides a means to investigate the electronic local density of states (LDOS) with subnanometer resolution. Atomic force microscopy (AFM) facilitates investigations of surface topography, local mechanics and a variety of other physical properties. The application of scanning probe microscopy in liquid (in-situ) and electrochemical (EC-SPM) environments enables nanoscale studies at the solid-liquid interface. The attractive nature of EC-SPM lies in its ability to control surface electronic properties while imaging redox active atomic and molecular systems. Instrumentation development relies on a sound understanding of the inherent strengths and limitations for a given technique. In an attempt to improve on currently available technology, this work has set out to employ creative approaches toward the design and construction of an EC-SPM that exceeds the performance, versatility, and mechanical stability of previously reported designs. The system described herein has been optimized for flexible low-noise SPM imaging in ambient, liquid, and electrochemical environments. Successful atomic resolution imaging by both STM and AFM modalities has been achieved. The application of STM to the study of three distinct organic molecular adsorption systems has been carried out in both electrochemical and ultra-high vacuum (UHV) environments. In all three cases, the cumulative interactions between the surface, adsorbate and probe tip provide insight into those forces that govern the properties of nanoscale systems. The controlled assembly of functional architectures and device at the molecular scale requires a thorough understanding of the delicate balance that this work has sought to probe.