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We report the synthesis of two palladium 2-(dialkylphosphino)­imidazole complexes and demonstrate their activity as catalysts for Suzuki–Miyaura reactions with (hetero)­aryl chlorides at room temperature. Our mechanistic studies demonstrate that these palladium complexes exist as an equilibrium mixture between the P–N coordinated and N–H NHC forms of ligand. Our studies suggest that the N–H NHC form may be important for high catalytic activity in Suzuki–Miyaura reactions with aryl chlorides. These reactions proceed at or near room temperature in good to excellent yields. Heteroaryl chlorides are also reactive at lower catalyst loadings.