Photoluminescent nanofibers (PLN) can be formed by combining electrospun polymeric nanofibers and luminescent particles such as quantum dots (QD). The physical properties of PLNs are dependent upon many different nanoscale parameters associated with the nanofiber, the luminescent particles, and their interactions. By understanding and manipulating these properties, the performance of the resulting optical structure can be tailored for desired end-use applications. For example, the quantum efficiency of quantum dots in the PLN structure depends upon multiple parameters including quantum dot chemistry, the method of forming the PLN nanocomposites, and preventing agglomeration of the quantum dot particles. This is especially important in solution-based electrospinning environments where some common solvents may have a detrimental effect on the performance of the PLN. With the proper control of these parameters, high quantum efficiencies can be readily obtained for PLNs. Achieving high quantum efficiencies is critical in applications such as solid-state lighting where PLNs can be an effective secondary conversion material for producing white light. Methods of optimizing the performance of PLNs through nanoscale manipulation of the nanofiber are discussed along with guidelines for tailoring the performance of nanofibers and quantum dots for application-specific requirements.