Along with growing public concerns over the energy crisis, hybrid and plug-in electric vehicles (HPEVs) are becoming increasingly popular. However, the total carbon footprint cannot be significantly reduced yet due to the relatively high carbon footprint of batteries in HPEVs. On-board PV systems, which mount PV cells on hood, roof, trunk, and door panels of an HPEV, can assist propelling the vehicle and enable battery charging whenever there is sunlight, and therefore, better mileage can be achieved for HPEVs. A reconfigurable on-board PV system has been proposed to tackle the output power degradation under a non-uniform distribution of solar irradiance levels on different vehicle panels. However, there are still some limitations for mounting PV cells on HPEVs even with the reconfiguration technique such as low efficiency, high cost, and appearance. To address these limitations, we propose to use semiconductor nanomaterials-based luminescent solar concentrators (LSC)-enhanced PV cells for the reconfigurable on-board PV systems. We properly optimize the size of the LSC-enhanced PV cell, the size of macrocells, and the reconfiguration period to achieve a balance between system performance and computation complexity, energy overhead, and capital cost. Furthermore, due to the transparency and flexibility of LSC polymer, we consider employing LSC-enhanced PV cells on vehicle windows. Experiments demonstrate up to 2.49× performance improvement of the proposed LSC-based PV system comparing with the baseline PV system.