The multichannel reaction of the C2Cl3 radical with O-2 has been studied thoroughly by step-scan time-resolved Fourier transform infrared emission spectroscopy. Vibrationally excited products Of Cl2CO, CO, and CO2 are observed and three major reaction channels forming respectively CICO + Cl2CO, CO + CCl3O, and CO2 + CCl3 are identified. The vibrational state distribution of the product CO is derived from the spectral fitting, and the nascent average vibrational energy of CO is determined to be 59.9 kJ/mol. A surprisal analysis is applied to evaluate the vibrational energy disposal, which reveals that the experimentally measured CO vibrational energy is much more than that predicted by statistical model. Combining previous ab initio calculation results, the nonstatistical dynamics and mechanism are characterized to be barrierless addition-elimination via short-lived reaction intermediates including the peroxy intermediate C2Cl3OO* and a crucial three-member-ring COO intermediate.