AbstractPalladium acetate reacts with 1‐benzyl‐3‐(2‐hydroxy‐2‐phenylethyl)‐1H‐imidazolium chloride to give the corresponding bis(carbene)palladium(II) complex 5 [(NHC)2PdCl2] by direct metalation. The X‐ray diffraction structure of the complex is reported. In the presence of NaOH solution (50 % H2O, w/w) in air and under microwave irradiation, the bis(NHC)pallalium(II) complex 5 is an active precatalyst for the Hiyama coupling of aryl halides with trialkoxy(aryl)silanes, providing biaryls and heterobiaryls. For some deactivated aryl bromides and for aryl chlorides, the corresponding cross‐coupling reactions require tetrabutylammonium bromide (TBAB) as additive. The fluoride‐free Hiyama reactions are performed with low (NHC)palladium loadings (0.1 mol‐%). The active catalyst can also be prepared in situ from Pd(OAc)2 and the corresponding imidazolium salt 4.