N-(3-Chloro-2-quinoxalinyl)-N′-arylimidazolium salts (aryl = 2,6-diisopropylphenyl [HL1Cl]Cl, aryl = mesityl [HL2Cl]Cl) have been synthesized by treating 2,3-dichloroquinoxaline with the corresponding N′-arylimidazole in neat water. Facile reactions of these imidazolium salts with Pd(PPh₃)₄ and Pd₂(dba)₃/PPh₃ (dba = dibenzyledene acetone) at 50 °C have afforded zwitterionic palladium(II) complexes [Pd(HL1)(PPh₃)Cl₂] (I) and [Pd(HL2)(PPh₃)Cl₂] (II) in excellent yields. I and II have been tested for their ability to catalyze Suzuki–Miyaura cross coupling (SMC) reactions in neat water/K₂CO₃ and are found to be highly active for carrying out these reactions between aryl bromides and organoboron reagents. Furthermore, the scope of the catalyst I was also examined by employing (hetero)aryl bromides, hydrophilic aryl bromides, benzyl bromides and various organoboron reagents. More than 80 aryl/benzyl bromide-arylboronic acid combinations were screened in neat water/K₂CO₃ and it was found that I was a versatile catalyst, which produced biaryls/diarylmethanes in excellent yields. A TON of 82 000 was achieved by using I. Studies on the mechanism have also been carried out to investigate the involvement of carbene complexes in the catalytic path. Poison tests and a two-phase test were also conducted and the results are reported.