Cyclometalated N-heterocyclic carbene (NHC) complexes possess fascinating electronic and catalytic properties. A series of cyclometalated iridium(III) complexes have been synthesized from the corresponding imidazolium salts via the aryl sp2 CH bond activation at the N1-phenyl/N3-benzyl wingtips of the imidazolylidene moiety. The electronic tuning towards the competitive formation of cyclometalated complexes (sp2 phenyl CH activation vs sp2 benzyl CH activation) has been discussed. These complexes have been utilized for the transfer hydrogenation (TH) reaction of 4-bromobenzaldehyde and 4-bromoacetophenone. These complexes showed excellent yields of the aryl-alcohols from 4-bromobenzaldehyde or 4-bromoacetophenone.