The temperature dependence of the photoluminescence (PL) of the rare-earth ion activated Y2SiO5 was investigated from room temperature to 573 K. Ion activators such as Eu-3+, Ce3+, Sm3+, Tb3+ and some of their combinations were studied in this study. The most efficient blue, green and red phosphors at elevated temperature were found by doping the (Ce3+ + Tb3+), Tb3+ and Eu3+ respectively, in this material system. Meanwhile, the relationship between the structure and the temperature dependence of the PL in RexY2-xSiO5 was also discussed.