We report the synthesis of micron‐sized vesicles of carbon encapsulating In2O3 nanocrystals, as well as neat In2O3 nanocrystals. The thermal decomposition of In(acetate)3 was carried out at 800 °C in air. This reaction was carried out under the autogenic pressure of indium acetate. The synthesized products were systematically characterized by X‐ray powder diffraction, scanning electron microscopy, and transmission electron microscopy. Carbon microvesicles, with an average diameter of 5 μm, encapsulated several nanometric‐sized In2O3 nanocrystals, as evidenced by high resolution transmission electron microscopy. The UV/Vis absorption of In2O3 nanocrystals was studied to estimate the bandgap energies. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)