Carbon nanotube (CNT) surface chemistry and surface structures impact their potential roles in photovoltaics in a number of ways.  These include defining chirality-specific segregation behaviors that enable isolation of the required pure chiralities.  Surface structures also define film morphologies and ordering that ultimately determine how intertube interactions facilitate or inhibit charge and energy flow.  We present photoluminescence imaging results as a direct probe of these relevant surface structures. A demonstration of phase-dependent segregation in surfactant compositions at the nanotube surface will be shown as a determining factor in the mechanism of new aqueous two-phase separations approaches.  We will also show how variations in polyfluorene polymer structures impact their surface morphologies, ultimately determining the ability to transport excitation energy and charge within thin-film nanotube-based PV devices.