Pyrochlore-structured Y2Ti2O7 doped with Eu3+ activators via high-temperature solid-state reaction shows thermally stable orange-red emission under near ultraviolet excitation. The concentration of Eu3+ activators was observed to influence both the intensity and color point of photoluminescence of Y2−xTi2O7:xEu3+ phosphors. The optimal doping concentration is around x = 0.45 determined by photoluminescence intensity; at this concentration, the luminescence branch ratio , named as the luminous intensity ratio of 5D0–7F2 (R) and 5D0–7F1 (O) transition is also at maximum, about 0.46. This orange–red emitting phosphor Y1.55Ti2O7:0.45Eu3+ shows excellent thermal stability in luminescence intensity, retaining 84% of room-temperature luminescence at 250°C. Therefore, Y1.55Ti2O7:0.45Eu3+ phosphors may have great potential as an orange–red component for white light-emitting diodes, especially for the high-power devices.