Photovoltaic (PV) performance is dependent on device operating temperature. We show that luminescent solar concentrators (LSCs) redistribute absorbed radiation and thermalization losses away from the photovoltaic cell to the waveguide in an LSC, keeping the PV cell cooler. Here we compare PV operating temperatures in an LSC compared to a conventional planar absorber PV device. We further examine the effects of PV cell orientation and luminophore properties within the LSC waveguide on PV temperature. By modeling LSC module efficiencies, we finally analyze the effects of various LSC system configurations on PV performance, and suggest optimal luminophore designs to improve PV temperature coefficients.