Abstract The kinetics of the of CCl2 with nitric oxide has been studied using the laser photolysis/photoionization mass spectrometry technique. Dichloromethylene biradicals were produced by the pulsed laser photolysis of carbon tetrachloride and the kinetics of their decay due to reaction with NO were monitored in direct time-resolved experiments. The temperature dependence of the rate constant (300–750 K) can be described by the Arrhenius expression k 1 =(1.12±0.18)×10 −12 exp (−(312±74) K/T ) cm3 molecule−1 s−1. Rate constants are independent of the bath gas density within the experimental range, [He] = (3–12) × 1016 atom cm−3. ClCNO was observed as a product of the reaction.