We report in detail the synthesis and characterization of V-shaped IrO2 nanowedges (NWs) with an angle of 110° between the two arms. The NWs were grown on top of rutile (R) phase TiO2 nanorods (NRs) sitting on a sapphire (SA)(100) substrate via metal-organic chemical vapor deposition (MOCVD) by using (C6H7)(C8H12)Ir and titanium-tetraisopropoxide (TTIP, Ti[OCH(CH3)2]4) as the source reagents. The surface morphology, structural, and spectroscopic properties of the as-deposited nanocrystals (NCs) were characterized by field emission scanning electron microscopy (FESEM), x-ray diffraction (XRD), micro-Raman spectroscopy, transmission electron microscopy (TEM), and selected-area electron diffractometry (SAED). The FESEM images and XRD patterns indicated growth of V-shaped IrO2(101) NWs on top of R-TiO2 NRs. The Raman spectrum showed the nanosize induced redshift and peak broadening of the IrO2 and rutile phase of TiO2 signatures with respect to that of the bulk counterparts. TEM and SAED characterizations of IrO2 NCs showed that the nanowedges were crystalline IrO2 with a twin plane of (101) and twin direction of at the V-junction. The probable mechanisms for the formation of well-aligned IrO2 NWs are discussed.