MgO surface makes it easy to introduce a certain amount of oxygen vacancy and can enhance catalytic reaction activity. Besides, as a silicoaluminate mineral material, halloysite nanotube (HNT) has a unique tubular structure. In this paper, the HNTs@MgO composite was successfully synthesized based on natural clay material HNTs as a carrier, and the CTL sensor based on HNTs@MgO was successfully developed for the rapid determination of ether in air. The HNTs@MgO material was characterized by a series of means such as SEM, XPS, and XRD, which clearly confirmed that MgO successfully combined with HNTs. And the sensor showed good sensitivity and selectivity, with a good linear relationship between CTL intensity and ether concentration in the range of 0.5–190.0 mg/L (R2 = 0.9942), and the limit of detection (LOD) was 0.18 mg/L (S/N = 3). The RSD values of the results of 11 consecutive measurements by the same sensor and 7 days of consecutive measurements were 1.96% (n = 11) and 3.42% (n = 7), showing good repeatability and reproducibility. At last, the CTL sensor was used to detect air samples, the recoveries ranged from 91.6% to 109.6%. Thus, it was concluded that HNTs@MgO composite is a cost‐effective and promising material with potential application in atmospheric detection.