The transparent glass–ceramics with Dy3+ and/or Sm3+ doping, which include the NaGd(MoO4)2 single‐crystal phase, were synthesized using the melt‐quenching method followed by heat treatment in the SiO2–B2O3–Na2O–ZnO–MoO3–Gd2O3 system. The formation and fluorescent properties of Dy3+ single‐doped precursor glasses were thoroughly examined, and the optimal doping amount of Dy2O3 was determined to be 0.3 mol% by fluorescence spectroscopy. The ideal heat treatment procedure for glass–ceramics containing Dy3+ and Sm3+ was determined to be crystallized at a temperature of 650°C for a duration of 7 h. After undergoing heat treatment, the luminescence performance of glass–ceramic is significantly boosted, exhibiting an improvement that is roughly twice as substantial when compared to the precursor glass. Extensive research has been conducted to thoroughly examine the fluorescence capabilities of glass–ceramics doped with both Dy3+ and Sm3+, and the intricate mechanism of energy transfer has been extensively explored. The transparent glass–ceramics doped with Dy3+ and Sm3+ and containing NaGd(MoO4)2 crystal phase can produce tunable luminescence from yellow to orange with a high color purity and a low correlated color temperature, which indicates that they have the potential to be applied to warm white light scenes such as household lighting under ultraviolet excitation.