Homocoupling of aryl iodides catalyzed by cyclopalladated complexes of tertiary arylamines gives symmetric biaryls with good yields in DMA or ionic liquid [Bmim]BF4. This catalytic alternative of the Ullmann reaction has proved to be sensitive to both electronic and steric factors of substrates. Homocoupling of aryl iodides catalyzed by cyclopalladated complexes of tertiary arylamines gives symmetric biaryls with good yields in DMA or ionic liquid [Bmim] BF4. This catalytic alternative of the Ullmann reaction has proved to be sensitive to both electronic and steric factors of substrates.