The utilization of nanostructured materials in electrochemical systems for energy conversion and catalysis has shown great promise. Fundamental studies into these systems are challenging, however, due to their inherently heterogeneous nature. Variations in particle size, shape, coupling, etc. can complicate the interpretation of experimental results. While electroanalytical and optical detection schemes have been employed to study electrochemical reactions occurring at individual nanostructures, reported approaches are severely limited by sample throughput and/or assumptions necessary for data analysis. Herein, the use of a combined electrochemical and optical approach to the study of these systems is described. Scanning electrochemical cell microscopy is employed to directly measure the rate of electrochemical reactions at individual nanostructures, while optical spectroscopy is used to probe the geometry of these nanostructures in situ. This complementary approach allows for the correlation of reliable electrochemical kinetic data with structural information and for the effects of photoexcitation on electrochemical reaction rates to be examined in a direct, quantitative manner. Initial studies applying this methodology to model electrocatalytic and photoelectrochemical systems will be presented.