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Growth of ternary AlGaN nanowires using metalorganic chemical vapor deposition is investigated. Structural, chemical, and optical characterization at nanoscopic scale is carried out by high resolution transmission electron microscopy, x-ray energy dispersive spectroscopy, and spatially resolved cathodoluminescence. Spontaneous formation of Al (Ga) NGaN coaxial nanowires with distinct emission at 370 nm is observed. It is identified that the interplay between surface kinetics and thermodynamics facilitates the catalytic growth of GaN core while a limited surface diffusion of Al adatoms leads to nonselective, vapor-solid growth of Al(Ga)N sheath. The observation points to a fundamental difference in nanosynthesis using near-equilibrium and nonequilibrium techniques. © 2005 American Institute of Physics.