Ornithogenic soils rich in phosphorous are widespread in Maritime Antartica, but the phosphatization process in these soils has not been fully considered as a primary soil-forming process in this cold region. This study present a detailed analytical, micropedological and submicroscopical characterization of a toposequence of ornithogenic soils in the vicinity of Arctowski Station, representing sucessive cycles of penguin nesting in the area. SED/EDS and WDS electron microprobe studies were carried out at high magnification. Basic soil chemical data of selected soil attributes shows great enrichment of P, Ca, K and other elements in ornithogenic soils. A granular, sub-rounded structure occurs in all ornithogenic horizons, with varying proportion of coarse fragments, and made of silty partcicles surrounded by phosphate illuvial deposition. These illuviation features characterize a distinct process of phosphatization, with P mobility and neoformation of uncommon secondary phosphates, such as Minyulite and Leucophosphite. Formation of Al-phosphates is related to different poorly crystalline Al forms down the profile, whereas K-Al phosphates are associated with younger leacheates in the upper parts of the ornithogenic soils. WDS and EDS data for the phosphatic plasma are consistent with its illuvial nature.