CdSe/CdS core/shell quantum dots (QDs) have been optimized toward luminescent solar concentration (LSC) applications. Systematically increasing the shell thickness continuously reduced reabsorption up to a factor of 45 for the thickest QDs studied (with ca. 14 monolayers of CdS) compared to the initial CdSe cores. Moreover, an improved synthetic method was developed that retains a high-fluorescence quantum yield, even for particles with the thickest shell volume, for which a quantum yield of 86% was measured in solution. These high quantum yield thick shell quantum dots were embedded in a polymer matrix, yielding highly transparent composites to serve as prototype LSCs, which exhibited an optical efficiency as high as 48%. A Monte Carlo simulation was developed to model LSC performance and to identify the major loss channels for LSCs incorporating the materials developed. The results of the simulation are in excellent agreement with the experimental data.