We examine the role of solution-phase polymer geometries on the favorability of forming oriented nanostructures from single conjugated polymer molecules formed from microdroplets of ultradilute solution. To our knowledge, this is the first time single molecule fluorescence correlation spectroscopy has been used to extract structural information from solution-phase fluorescence measurements. We find that production of oriented species is strongly favored in "poorer" solvents, where the polymer chains have more compact solution-phase structures. While charging during droplet generation is essential for orientation, we conclude that most of the internal organization associated with these interesting structures takes place in solution, independent of the droplets.