Ni(ii)-tetradentate amido-quinoline complexes effectively catalysed C-H chlorination of a series of hydrocarbons in the presence of NaOCl and acetic acid. The bond dissociation energy of the C(sp3)-H bond of the substrates varies from 99.3 kcal mol−1 (cyclohexane) to 87 kcal mol−1 (ethyl benzene). Exclusively chlorinated products (TON: 220 for cyclohexane) were obtained without any hydroxylated products, thus mimicking the activity of the halogenase enzyme. © 2022 The Royal Society of Chemistry