With the readily available Gorlos-Phos as a ligand, unsymmetrical biaryls were prepared efficiently from Pd-catalyzed one-pot two-step cross-coupling of two different aryl chlorides in the presence of B₂Pin₂, tolerating functional groups such as aldehyde, ketone, ester, ether, nitrile, amide, fluorine, sulphonyl and trifluoromethyl groups. Besides the substituted phenyl chlorides, hetero-aryl chlorides, 1-chloronaphthalene, and dichlorobenzenes could also be applied. The cytotoxicity against human lung cancer A549 cells for some of the compounds has been studied.