Using electrochemistry to enact organic molecule transformations offers a potential route towards greener chemical manufacturing. However, such reactions can often be complex with a multitude of factors at play. In their Communication (e202509115), Yanwei Lum et al. performed a systematic study of the impact of electrolyte cations on the selectivity of electrochemical C─H chlorination of cyclohexane. It was found that larger cations increase the propensity towards the formation of chlorine radicals, which then facilitates the formation of chlorocyclohexane through a radical non-chain mechanism.