The non-centro-symmetric semiconductor BiTeI exhibits two distinct surface terminations that support spinsplit Rashba surface states. Their ambipolarity can be exploited for creating spin-polarized p-n junctions at the boundaries between domains with different surface terminations. We use scanning tunneling microscopy (STM) and spectroscopy (STS) to locate such junctions and investigate their atomic and electronic properties. The Te-and I-terminated surfaces are identified owing to their distinct chemical reactivity and an apparent height mismatch of electronic origin. The Rashba surface states are revealed in the STS spectra by the onset of a van Hove singularity at the band edge. Eventually, an electronic depletion is found on interfacial Te atoms, consistent with the formation of a space-charge area in typical p-n junctions. In inversion-asymmetric systems, the spin-orbit interaction lifts the spin degeneracy. This effect can occur either at surfaces (the Rashba-Bychkov effect [1]) or in the bulk of non-centro-symmetric crystals (the Rashba-Dresselhaus effect [2,3]). Such Rashba systems are promising candidates for manipulating electron spin by means of electric field in the context of emerging spintronic devices [4]. Significant research efforts are currently directed toward the search of materials exhibiting a "giant" Rashba effect that would enable nanometer-scale spintronic devices operating at room temperature. To date, the largest spin splitting, measured by angle-resolved photoemission spectroscopy (ARPES), has been reported in the BiAg 2 /Ag(111) surface alloy [5] and both the surface and bulk states of non-centro-symmetric semiconductor BiTeI [6][7][8][9].In BiTeI, photoemission data show two distinct types of surface domains with different surface terminations (Te and I) and opposite surface band bendings that support p-or n-type surface states [8]. We anticipate that Rashba p-n junctions can be observed at the boundaries between such domains. This can be used for fulfilling another requirement for fabricating logic devices-ambipolarity, which is the possibility to control carriers' nature (electrons or holes). Moreover, a number of novel transport phenomena have been predicted for p-n junctions in systems with strong spin-orbit coupling [10][11][12][13] that can be further exploited in practical applications. In view of applications, the questions of current dissipation to the bulk or controlled growth of the junction by epitaxy are important, but well beyond the scope of this paper. Here, cleaved BiTeI is rather considered as a toy-system providing a quite unique opportunity to study a p-n junction in two dimensions.In this work, we employ scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) to locate and investigate p-n junctions naturally occurring at a cleaved BiTeI surface. The surface domains with Te and I terminations are identified owing to their distinct chemical reactivity, apparent height, and electronic structure. The onset of a van * cedric.tournier@epfl.ch Hov...