NaGdF 4 nanocrystals of the hexagonal β-phase can be prepared with very narrow size distribution from small particles of the cubic α-phase of NaGdF 4 , but, until now, this method does not allow to control the final particle size. Here we show that the size of β-NaGdF 4 particles can be varied between 4 nm and more than 60 nm by using small α-phase particles with different sodium content as precursor. Heating of the 3-4 nm α-phase particles dispersed in oleic acid/octadecene solvent leads to Ostwald ripening and the formation of β-NaGdF 4 particles with narrow size distribution in all cases. The size of the β-NaGdF 4 particles increases with increasing sodium deficiency of the α-phase particles indicating that the number of β-phase seeds nucleating in the system depends on the ratio of sodium to gadolinium used in the synthesis of the α-phase material.