BiInO3 is a potentially polar oxide with distinct optical properties whose origin could result from a surface that has not been well characterized. The surface properties of BiInO3 thin films have been characterized here by temperature dependent angle-resolved x-ray photoemission spectroscopy. A large surface to bulk core-level binding energy shift for the In 3d5/2 core-level is identified, indicating a surface very different from the bulk. BiInO3 terminates in indium oxide and loses bismuth from the surface of the film at T = 573 K. The Debye–Waller plots suggest effective Debye temperatures of 263 ± 10 and 556 ± 27 K for the surface and bulk components of In 3d core-level, respectively.