AbstractA simple new protocol for the palladium‐catalyzed Suzuki–Miyaura cross‐coupling of organic chlorides under microwave irradiation is presented. Deactivated aryl and heteroaryl chlorides are efficiently cross‐coupled with alkenylboronic acids and potassium alkenyltrifluoroborates using the 4,4′‐dichlorobenzophenone oxime‐derived palladacycle 1b as precatalyst in 0.1 to 0.5 mol% palladium loading, tris(tert‐butyl)phosphonium tetrafluoroborate {[HP(t‐Bu)3]BF4} as ligand, tetra‐n‐butylammonium hydroxide as cocatalyst, and potassium carbonate as base in N,N‐dimethylformamide at 130 °C under microwave irradiation conditions. Under these conditions, styrenes, stilbenes, and alkenylarenes are obtained in good to high yields, and with high regio‐ and diastereoselectivities in only 20 min. The reported protocol is also very efficient for the regioselective alkenylation of benzyl and allyl chlorides to afford allylarenes and 1,4‐dienes.