High‐sensitive detection of NO is very important to protect environment and human health. In this study, the composites of ZnO nanorods and CsPbBr3/Cs4PbBr6 particles are synthesized successfully and used as sensing materials for detection of NO, in which the as‐prepared samples exhibit ultra‐high response and excellent selectivity to NO at 50 °C. Toward 100 ppm NO, the response is up to about 2296. The samples can high‐sensitively detect 1 ppm NO with response of about 6, demonstrating a low detection limit. The high response of CsPbBr3/Cs4PbBr6/ZnO could be attributed to the multiple heterojunctions formed among three materials. The results demonstrated that the composites of CsPbBr3/Cs4PbBr6 and ZnO should be a promising material for preparing the high‐sensitive NO sensors at low temperature. [ABSTRACT FROM AUTHOR]