The IrIII compound [TpMe2Ir(C6H5)2(N2)] (1) [TpMe2 = hydridotris(3,5‐dimethylpyrazolyl)borate] reacts with 1‐hexene, propene, α‐methylstyrene, and 2,3‐dimethylbutadiene to yield organometallic products that derive from allylic C–H activations (complexes 3 from 1‐hexene, 2 from propene, 5 from α‐methylstyrene, and 7, 8, and 9 from 2,3‐dimethylbutadiene), in all cases along with organic products formed in catalytic (Ir‐induced) dehydrogenative coupling of benzene (the solvent of the reaction) and the corresponding olefin, with the latter also acting as the hydrogen scavenger in each case. Differently, complex 1 reacts with (E)‐β‐methylstyrene and cyclohexadiene to yield complex 2 and the known (η4‐cyclohexadiene)IrI derivative 6, respectively. Finally, compound 1 reacts under mild conditions with cyclopentadiene and methylcyclopentadiene with the generation of phenyl derivatives 11 and 12 in which the corresponding cyclopentadienyl ligand adopts the η5 coordination and forces the TpMe2 ligand to coordinate in the κ2 mode.