Carbon monoxide (CO), as a dangerous emission gas, is easy to accumulate in the complex underground environment and poses a serious threat to the safety of miners. In this paper, a sensor using a quantum cascade laser with an excitation wavelength of 4.65 μm as the light source, and a compact multiple reflection cell with a light path length of 12 m is introduced to detect trace CO gas. The sensor adopts the long optical path differential absorption spectroscopy technique (LOP-DAST) and obtains minimum detection limit (MDL) of 108 ppbv by comparing the residual difference between the measured spectrum and the Voigt theoretical spectrum. As a comparison, the MDL of the proposed sensor was also estimated by Allan deviation; the minimum value of 61 ppbv is achieved while integration time is 40 s. The stability of the sensor can reach 2.1 × 10−3 during the 2 h experimental test and stability of 1.7 × 10−2 can still be achieved in a longer 12 h experimental test.