The In 3d(5/2) photoelectron spectroscopy peak has been widely used to determine the interface structures of In-containing III-V device materials (e.g., oxidation states). However, an unclear parameter affecting the determination of the energy shifts and number of the core-level components, and therefore, the interpreted interface structure and composition, is still the intrinsic In 3d(5/2) peak line shape. It is undecided whether the line shape is naturally symmetric or asymmetric for pure In-containing III-V compounds. By using high-resolution photoelectron spectroscopy, we show that the In 3d(5/2) asymmetry arising from the emission at high binding-energy tail is not an intrinsic property of InAs, InP, InSb and InGaAs. Furthermore, it is shown that asymmetry of In 3d(5/2) peaks of pure III-V's originates from the natural surface reconstructions which cause the coexistence of slightly shifted In 3d(5/2) components with the symmetric peak shape and dominant Lorentzian broadening. (C) 2015 Elsevier B.V. All rights reserved.