The effects of excitation wavelength on the optical properties (emission spectrum and quantum yield) of a luminescent solar concentrator (LSC) containing a fluorescent organic dye (Lumogen F Rot 305) are studied. Excitation at wavelengths on the long-wavelength edge of the absorption spectrum of the dye results in redshifted emission, but the quantum yield remains constant at 100%. The origin of this effect and its consequences are discussed. The extent of the long-wavelength tail of the absorption spectrum of the dye is determined and the importance in reabsorption losses is shown. The optical efficiencies and photon transport probabilities of LSCs containing either an organic dye or a rare-earth lanthanide complex are compared using ray-tracing simulations and experiment. The optical efficiency is shown to depend strongly on the Stokes shift of the fluorophore. The lanthanide complex, which has a very large Stokes shift, exhibits a higher optical efficiency than the dye (64% cf. 50%), despite its lower quantum yield (86% cf. 100%). © 2010 Optical Society of America.