Exploring new, efficient, and stable phosphors is important and meaningful work for both LEDs and FEDs. Here, the new Ce3+/Tb3+-codoped green-emitting phosphor Sr2LiScB4O10 with high energy transfer efficiency and outstanding stability was designed and prepared by a solid-state reaction. The phosphors show a broad excitation spectrum in the range of 235-375 nm and a narrow green emission spectrum around 544 nm. The strong Tb3+ emission with weak Ce3+ emission and the decreasing lifetime of Ce3+ indicate that the samples have high energy transfer efficiency up to more than 90%. The green emission intensity at 250 °C can keep 75% of its intensity at room temperature with changeless color coordinates, which reveals that the phosphors have excellent thermal stability and color stability. The CL performance indicates that the phosphor possesses high saturation current and saturation voltage with good color stability, and a related luminescence mechanism was proposed to explain the remarkable CL properties. On the basis of the outstanding luminescence performance and thermal and color stability in PL and CL, the phosphor shows promise for applications in LEDs and FEDs.