Tetrakis(dimethylamino)ethylene (TDAE)/cat. PdCl2(PhCN)(2)-promoted reductive coupling of aryl bromides having either electron-donating or electron-withdrawing groups on their para- and/or meta-position proceeded smoothly to afford the corresponding biaryls in good to excellent yields. Notably, TDAE is such a mild reductant that easily reducible groups, such as carbonyl and nitro groups, are tolerate. A similar reductive coupling of ortho-substituted aryl bromides did not occur at all. The proper choice of palladium catalysts is essential for the reductive coupling; thus, PdCl2(PhCN)(2), PdCl2(MeCN)(2), Pd(hfacac)(2), Pd-2(dba)(3), PdCl2, and Pd(OAc)(2) were used successively for this reaction, but phosphine-ligated palladium catalysts such as Pd(PPh3)(4), PdCl2(PPh3)(2), and Pd(dppp) did not promote the reaction. The reductive coupling did not occur with nickel catalysts such as NiBr2, NiCl2(bpy), and Ni(acac)(2). The TDAE/cat. palladium-promoted reductive coupling of aryl halides having electron-withdrawing groups took place more efficiently than that of aryl halides substituted with electron-donating groups. A plausible mechanism of TDAE/cat. palladium-promoted reaction is discussed.