NaYF4:Eu3+ core and NaYF4:Eu3+/NaYF4 core/shell nanocrystals (NCs) were synthesized via a wet chemical method. The transmission electron microscope photographs show that the core and core/shell nanoparticles are monodisperse and uniform NCs with average diameters of 22 and 26 nm respectively. The photoluminescence (PL) properties of the samples, including the PL excitation and emission spectra, and luminescent decay curves, are investigated in detail. The results show that the intensity of 5D2 emission relative to that of 5D0 is stronger in NaYF4:Eu3+/NaYF4 core/shell NCs than that in NaYF4:Eu3+ core NCs, and a longer decay lifetime of 5D2 is observed in core/shell samples. In addition, from the corrected emission spectra of 5D0, the 5D0 radiative lifetimes were calculated. These together with the measured decay lifetime of 5D0 emission give the intrinsic quantum yields of 5D0. The results were well interpreted by considering the surface effects.