Three doubly ordered double perovskites NaREMgWO6 (RE = La, Gd, Y) have been synthesized via traditional solid-state methods, doped with Eu3+, and characterized to evaluate their promise as Eu3+ phosphor hosts. NaYMgWO6, a new member of the family, was found to crystallize in the P2(1) space group and is isostructural with NaGdMgWO6. Emissions characteristic of Eu3+ ions (D-5(0) -> F-7(4,3,2,1,0)) were observed, with the most intense transition being the D-5(0) -> F-7(2) transition near 615 nm. Substitution of Eu3+ onto a more compressed RE site in the NaY1-xEuxMgWO6 and NaGd1-xEuxMgWO6 hosts results in a blue shift of the charge transfer excitation band and an increase in the intensity of the D-5(0) -> F-7(2) transition compared to NaLa1-x EuxMgWO6. All of the hosts can incorporate high concentrations of Eu3+ before concentration quenching is observed. When the rare-earth ion is either Gd3+ or Y3+, good energetic overlap between the Eu3+ charge-transfer band and the absorption of the host lattice results in sensitization and energy transfer from the perovskite host lattice to the Eu3+ activator sites. These hosts display comparable if not better luminescence than Y2O3:Eu3+, a commonly used commercial standard, demonstrating their promise as red phosphors.