Undoped and Eu3+-doped cubic yttria (Y2O3) nanophosphors of good crystallinity, with selective particle sizes ranging between 6 and 37 nm and showing narrow size distributions, have been synthesized by a complex-based precursor solution method. The systematic size tuning has been evidenced by transmission electron microscopy, X-ray diffraction, and Raman scattering measurements. Furthermore, size-modulated properties of Eu3+ ions have been correlated with the local structure of Eu3+ ion in different sized Y2O3:Eu3+ nanophosphors by means of steady-state and time-resolved site-selective laser spectroscopies. Time-resolved site-selective excitation measurements performed in the F-7(0) -> D-5(0) peaks of the Eu3+ ions at C-2 sites have allowed us to conclude that Eu3+ ions close to the nanocrystal surface experience a larger crystal field than those in the nanocrystal core. Under the site-selective excitation in the F-7(0) -> D-5(0) peaks, energy transfer between the sites has also been observed. (C) 2013 Published by Elsevier B.V.