The combination of Raman spectroscopy with electrochemical techniques is an attractive approach to studying microbial communities due to the blend of label-free molecular composition information with sensitive, inexpensive in situ monitoring of the redox states of target molecules. The work in this thesis focuses on the combined application of these tools to two disparate microbial systems. Pseudomonas aeruginosa is one of the major causes of hospital acquired infections, including those arising from cystic fibrosis, burn wounds, and organ transplants, leading to high rates of mortality and morbidity. Myxococcus xanthus is a common soil bacterium that exhibits various form of self-organizing behavior in response to changes in environment, for example, the development of multicellular fruiting bodies in response to constrained nutrient availability.A novel application of surface enhanced Raman scattering (SERS) coupled with electrochemical techniques is described to investigate the secretion of the virulence factor pyocyanin (PYO) by P. aeruginosa. Results from PYO were obtained in both model systems and secreted from P. aeruginosa in biofilms. Both reveal decreasing SERS intensities of PYO intensities under reducing conditions. Furthermore, SERS imaging indicates that secreted PYO is localized in regions approximately the size of P. aeruginosa cells, suggesting its localization in the biofilm environment.Other phenazines, including phenazine-1-carboxylic acid, 5-methyl-phenazine-1-carboxylic acid, and phenazine-1-carboxamide, have also been identified as secreted factors from P. aeruginosa. Electrochemical determination of these factors using nanopore electrode arrays (NEAs) has been demonstrated for enhanced detection of these phenazines, again using both model systems and P. aeruginosa bacteria. When bacterial cells are applied to the NEA surface, only phenazine molecules can diffuse into the nanopores, while bacteria are excluded due to their size. Thus, highly efficient redox cycling conditions can be accessed in the NEAs by free diffusion unhindered by the presence of bacteria. This strategy was used to demonstrate phenazine determinations with limits of detection, 10.5 nM and 20.7 nM for PYO and phenazine-1-carboxamide, respectively, ca. 100-fold lower than achievable by square wave voltammetry.Finally, this work discusses the confocal Raman microscope (CRM) application to examine M. xanthus DK1622 wild-type chemical signals and their fingerprints under various nutrient conditions. Spatial mapping of Raman features for DK1622 grown under both vegetative conditions and those that promote the formation of fruiting bodies was performed by combining CRM imaging with principal component analysis. Ten distinct spectral features were observed from M. xanthus grown on nutrient-rich CTT by CRM. When the DK1622 strain of M. xanthus was constrained to grow under nutrient-limited conditions, by starving it of casitone, it developed fruiting bodies, and the accompanying Raman microspectra exhibited distinct features, with the absence of casitone in the medium reducing, or completely eliminating, features at 1140 cm-1, 1560 cm-1 and 1648 cm-1. In their place a feature at 1537 cm-1 was observed, this feature being tentatively assigned to a transitional phase important for cellular adaptation to varying environmental conditions. While the metabolites responsible for these Raman features are not completely identified yet, three M. xanthus peaks at 1004 cm-1, 1151 cm-1, and 1510 cm-1 are consistent with the production of lycopene. Finally, spatial distribution of signals acquired from principal component heat maps indicate that the signaling molecules associated with fruiting bodies stay closely related with these structures throughout formation and maturation of these nutrient-directed structures.