A key challenge in nanotechnology and nanoscience is to connect local physicochemical material properties with macroscopic behavior; in particular, it is still not possible to interrogate and image the local chemistry of a surface. Toward that end, this dissertation highlights the design and implementation of a multiscale spectroscopy platform for chemical and optical interrogation of thin films at the diffraction limit (~300nm) and below (10's of nm). Design and validation of the instrument are discussed with quantitative emphasis on confocal microscope operation, multi-functional spectroscopic imaging at the diffraction limit, plasmonic enhancement by the tip, and Raman imaging of nanowires. This work also includes several spectroscopic studies on blends of conducting polymer and fullerene, a mixture used for solar energy applications. In particular, this work employs bulk absorption, photoluminescence (steady state and transient), and Raman spectroscopy to connect the effects of processing (composition, annealing, solvent, etc.) with the micro-morphology of polymer solar cell films. Additionally, confocal spectroscopic imaging of charge transfer excitons and other emission processes in polymer solar cells is used to directly probe phase separation which occurs during film annealing. The methods developed within this work are a generally applicable, facile way to understand the micro- and nanoscale morphology of polymer solar cells and other material systems.