We synthesized the tris-cyclometallated iridium complexes containing the substituted styryl groups and their saturated analogs. As the styryl iridium complexes, Ir(F-ppy-4-CH=CHC(6)H(4)R)(3) (where R = Me, NMe(2), OMe) were prepared via direct functionalization of the methyl groups in the ppy (2-phenylpyridine) ligand at the iridium complexes. The corresponding saturated analogs, Ir(F-ppy-4-CH(2)CH(2)C(6)H(4)R)(3) (where R = Me, NMe(2)), were synthesized during the two step reactions of the IrCl(3) center dot xH(2)O with F-ppy-4-CH=CHC(6)H(4)R via in situ hydrogenation. Their photophysical properties were investigated both in solution and in film. The longer pi-conjugation in the cyclometallating ligands leads to the bathochromic shift in photoluminescence of their iridium complexes. Among R groups, the NMe(2) end group had the strongest push-pull effect with the F group at the other end, and led to the effective control of the ILCT transition.