Synthesis of Plagiochins A and B, Macrocyclic Bis(bibenzyl) Ethers from Plagiochila acantophyllaPlagiochins A (1) and B (2), macrocyclic bis(bibenzyl) ethers with a 16‐membered ring, are synthesized. The key steps are the Pd(0)‐catalyzed C—C coupling of an areneboronic acid (18) with an aryl bromide with formation of a biphenyl (13), Ullmann ether synthesis of a diphenyl ether (23), Wittig reaction to connect the two components 13 and 23, and a modified Wurtz reaction to close the ring. The latter reaction is accompanied by an unusual transformation of a C‐benzyloxy to a C‐benzoyl group.