In situ techniques are indispensable to understanding many topics in surface chemistry. As a consequence, several spectroscopic methods have been developed to provide molecular-level information that only spectroscopy can supply. However, as important as this information is, it is just as critical to realize that nearly all surfaces under investigation have spatial heterogeneities of the order of nanometers to millimeters; thus, spatial analysis is very important to the overall interpretation. This Minireview focuses on a few of the recent developments in spectroscopic techniques that can provide spatial, spectroscopic, and in situ information. These techniques include photo-electron microscopy, infrared and Raman imaging, and nonlinear optical imaging vibrational spectroscopy as applied to topics in corrosion, catalysis and self-assembled monolayers.