Here, we investigate the effects of both tuning the range-separation parameter of long-range corrected (LRC) density functionals and including dispersion corrections on describing the local optoelectronic properties of polymer-fullerene interfaces that are critical to the performance of polymer solar cells (PSCs). Focusing on recently studied (Chen, et al., Chem. Mater., 2012, 24, 4766-4772) PSC active layers derived from poly(benzodithiophene-co-quinoxaline) and substituted fullerene PCBM, we compare the performance of global hybrid functionals (B3LYP and B3LYP-D) alongside two LRC functionals (ωB97X and ωB97X-D) and their optimally tuned (OT) analogs (OT-ωB97X and OT-ωB97X-D). Our results confirm that OT-LRC functionals generally improve the description of the optical properties of the individual materials with respect to experiment. For electron-donor (eD)-electron-acceptor (eA) complexes used to describe the local optoelectronic properties of the material interface, PCBM is found to preferentially settle near the quinoxaline acceptor units on the copolymer backbone, regardless of the functional, though dispersion corrections have a strong influence on the intermolecular distances and, in turn, the nature of the excited states. All functionals yield very similar descriptions of the transition maxima for the complexes, i.e. predominant local excitations on the copolymer. Importantly, tuning the range-separation parameter of the LRC functional is shown to have a profound effect, as the OT functionals allow for the description of the charge transfer states of the eD-eA complexes, while the non-tuned LRC functionals predict only local intramolecular excitations. These results hold considerable importance for deriving the appropriate physical understanding of the interfacial structure-property-function relationships of PSCs.