Inertness of the cleaved (0001) surface of the Bi2Se3 single crystal, grown by modified Bridgman method, to oxidation has been demonstrated by X-ray photoelectron spectroscopy, scanning tunneling microscopy, and by ab initio DFT calculations. No intrinsic bismuth and selenium oxides are formed on the low-defect, atomically flat Bi2Se3(0001)-(1 x 1) surface after a long-time air exposure. The inertness of Bi2Se3(0001) to O-2 and NO2, as well as bismuth-oxygen bonding formation under molecular adsorption in the Se vacancy was supported by DFT calculations. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4767458]