Abstract1,4‐Diazabicyclo[2.2.2]octane (DABCO) is a suitable Lewis base that acts as an organocatalyst in the activation of N‐chlorosuccinimide (NCS) towards the chlorination of alkenes. The chloriranium ion formed from NCS and the alkene, can be intermolecularly opened by a nucleophile, such as acetic acid, to produce highly functionalized trans‐chloro esters in high yields. The protocol is also applied to the synthesis of chlorohydrins and chloro ethers using water or methanol as nucleophiles instead of acetic acid. Brominated analogs can also be synthesized from alkenes and N‐bromosuccinimide (NBS) in the presence of various basic catalysts. However, the reaction patterns seem to be remarkably different. The catalytic performance of bases in the bromoesterification of alkenes was found to be strongly affected by their Brønsted basicity, suggesting that acetyl hypobromite, formed in situ from NBS and acetic acid, acts as a real brominating agent in these systems.magnified image