Hydrothermally prepared nanophosphor Y2SiO5:Ce crystallizes in the P21∕c structure, rather than the B2∕b structure observed in bulk material. Relative to bulk powder, nanophosphors of particle size ∼25–100nm diameter exhibit redshifts of the photoluminescence excitation and emission spectra, reduced self absorption, enhanced light output, and medium-dependent radiative lifetime. Photoluminescence data are consistent with reduced symmetry of the P21∕c structure and are not necessarily related to reduced dimensionality of the nanophosphor. In contrast, medium-dependent lifetime and enhanced light output are attributed to nanoscale behavior. Perturbation of the Ce ion electric field is responsible for the variable lifetime.