NaScMo2O8:RE3+ (RE = Tb, Eu, Tb/Eu, Yb/Er, Yb/Ho) phosphors were successfully synthesized by surfactant-free hydrothermal method and post-calcination treatment. The energy transfer (ET) of MoO4 (2-) -> Tb3+ -> Eu3+ was proved by photoluminescence spectra and decay features. Multicolor emissions (green -> yellow -> red) were obtained by adjusting the ratio of Tb3+/Eu3+ upon excitation into the MoO4 (2-) at 292 nm. The ET of Tb3+ -> Eu3+ was demonstrated to be a resonant type via a dipole-dipole mechanism, and the crystal distance (R (c)) was calculated by the quenching concentration method. Under 980 nm excitation, the emission of NaScMo2O8:RE3+ (RE = Yb/Er, Yb/Ho) showed strong green (Yb3+/Er3+: S-4(3/2), H-2(11/2) -> I-4(15/2); Yb3+/Ho3+: S-5(2) -> I-5(8)) luminescence, respectively. Moreover, the doping concentration of the Yb3+ has been optimized under a fixed concentration of Er3+ and Ho3+, respectively. The NaScMo2O8:RE3+ phosphors have potential applications for color displays and light-emitting devices due to a variety of luminous colors.