Demand for real‐time detection of hydrogen and ammonia, clean energy carriers, in a sensitive and selective manner, is growing rapidly for energy, industrial, and medical applications. Nevertheless, their selective detection still remains a challenge and requires the utilization of diverse sensors, hampering the miniaturization of sensor modules. Herein, a practical approach via material design and facile temperature modulation for dual selectivity is proposed. A Pd nanoparticles‐decorated W18O49 nanowire gas sensor is prepared for dual detection of hydrogen and ammonia. The sensor exhibits distinct operating temperatures for ultraselective detection of hydrogen (125 °C) and ammonia (225 °C), with high responses of 35.3 and 133.8, respectively. This dual selectivity with high sensitivity is attributed to enhanced oxygen adsorption, the chemical affinity of sensing materials for target gases, and distinct reactivity profiles of gases. The proposed sensor is further integrated into a microelectromechanical system, enabling its small size, low power consumption, and rapid temperature modulation. Moreover, the practical feasibility of this sensor platform for smart energy monitoring systems is demonstrated by assessing its sensing properties in electrochemical ammonia oxidation reaction systems. This work can provide a practical approach for developing a single gas sensor with multiple functionalities for application in electronic nose systems.