Cerium containing calcium sulfite hemihydrate, CaSOj:Ce -1/2H20, of spherical particles was prepared as start material by precipitation using a reaction between ammonium (1 -x)-sodium (x) sulfite solution (x = 0-64 mole percent) containing a given concentration of cerium sulfate (III), and a calcium chloride solution. This CaSOj:Ce -1/2H30 was reduced to cerium-activated calcium sulfide (CaS:Ce) of spherical particles in a stream of hydrogen sulfide at 900~ The relationships between the sodium (Na) content in both the starting material, CaSOj:Ce-1/2H20, and the reduction product, CaS:Ce, and the intensity of photoluminescenee was investigated. A linear relationship between the intensity of photoluminescence and the Na content up to about 0.3-0.4 mole percent (Na/CaS:Ce), where the intensity has its maximum, was observed. With increasing Na content in the CaSOj:Ce 9 1/2H20, the surface morphology of the CaS:Ce shows sintering, and fine particles become larger and well grown.Calcium sulfide (CaS) phosphors prepared by a sulfurizing flux method using a mixture of a calcium compound containing activator, Na~CO3 as flux, and an excess amount of sulfur has been reported before (1). Also CaS