This work proposed a novel strategy to fabricate highly-stable NO2 sensor based on a pyrochlore-phase Gd2Zr2O7 oxygen conductor. The incorporation of alkaline-earth metals distinctly enhances the sensing performance of the Gd2Zr2O7 based sensors. The excellent sensor based on Gd1.95Ca0.05Zr2O7+δ exhibits rapid response-recovery characteristics with the maximum response current value (ΔI = 6.4 μA), extremely short 90% responce (3 s) and 90% recovery (35 s) time towards 500 ppm NO2 at 500 °C, which is better than that of commercial YSZ under the same condition. The ΔI value towards NO2 is much higher than those towards other gases (CH4, C3H6, C3H8, CO, NO, SO2, C2H4, CO2 and C2H6), exhibiting excellent selectivity for detecting NO2. The response signal basically maintains a stable value of 6.4 μA after the sensors was stored for half a month and a month. The outstanding selectivity and highly stability of the NO 2 sensors based on Gd2-xMxZr2O7+δ are expected to a promising application in automotive vehicles.