Novel Ba 2 CaMoO 6 :Eu 3+ reddish orange phosphors were synthesized by the sol–gel method. The XRD results indicate that the phosphors keep the cubic structure. The excitation spectra exhibit an intense broad charge transfer (CT) band centered at 380nm, indicating the phosphors can be effectively excited by near UV (370–410 nm) light. The photoluminescence (PL) measurements demonstrate a strong red emission band centered at about 595nm ( 5 D 0 → 7 F 1 ) under host excitation at 380nm. A low concentration quenching occurs in Ba 2 CaMoO 6 :Eu 3+ and the optimal doping concentration is about 6mol%. The efficient energy transfer from host to Eu 3+ ions in Ba 2 CaMoO 6 :Eu 3+ phosphors has been discussed in this paper.