The performance of perovskite solar cells is strongly influenced by the composition and microstructure of the perovskite. A recent approach to improve the power conversion efficiencies utilized mixed-halide perovskites, but the halide ions and their roles were not directly studied. Unraveling their precise location in the perovskite layer is of paramount importance. Here, we investigated four different perovskites by using X-ray photoelectron spectroscopy, and found that among the three studied mixed-halide perovskites, CH3NH3Pb(I0.74Br0.26)3 and CH3NH3PbBr3-xClx show peaks that unambiguously demonstrate the presence of iodide and bromide in the former, and bromide and chloride in the latter. The CH3NH3PbI3-xClx perovskite shows anomalous behavior, the iodide content far outweighs that of the chloride; a small proportion of chloride, in all likelihood, resides deep within the TiO2/absorber layer. Our study reveals that there are many distinguishable structural differences between these perovskites, and that these directly impact the photovoltaic performances. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.