Chains of closely spaced metal or semiconductor particles have potential applications in optoelectronics and single electron devices. We report, for the first time, the synthesis of Ga2O3 chains with closely spaced knots connected by nanowires using the thermal evaporation method with a specially designed quartz boat. The Ga2O3 chains grew only on the Si substrates where An catalyst or Ga droplets were coated. The average diameter of the knots is about 450 nm and that of the nanowires is about 50 run. The selected area electron diffraction of either a knot or a connecting nanowire includes two sets of overlapped single crystal electron diffraction patterns which belong to the [10 2] and [10 T] crystal zone axes of the monoclinic beta-Ga2O3 phase, respectively. The knot and its neighbor nanowire have the common (2 0 1) growth planes at their interface. A mechanism model for the Ga2O3 chains synthesis based on the vapor-liquid-solid mechanism is discussed. (C) 2004 Elsevier B.V. All rights reserved.