Abstract: A new palladium catalyst system, generated in situ from palladium(II) chloride and hydroxynaphthalene‐2‐oxazolines as ligands, has been developed and used in Suzuki‐Miyaura cross‐coupling reactions with potassium heteroaryl‐ and aryltrifluoroborate salts to synthesize biphenyl derivatives in good to high yields. It was observed that the catalyst works only when generated in situ. When isolated the formation of a solid occurs which when subjected to x‐ray diffraction shows that the palladium atom is bound to two oxazolines. The presence of electron donor or electron withdrawals groups does not significantly affect reaction performance. This allows easy preparation for use without the inconvenience of catalyst decomposition and need for storage care. A plausible mechanism reaction was suggested based on HRMS studies. [ABSTRACT FROM AUTHOR]