Monolayer Fe films on Pt(111) and their derived structures under different environments were investigated by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). The growth of monolayer Fe films was seen at 487 K. The surface composition and structure of the Fe/Pt(111) surface were monitored by XPS and STM during stepwise annealing under vacuum. Surface Fe was driven into the subsurface region during annealing above 800 K. This resulted in a Pt-skin surface of Pt/Fe/Pt(111). Oxidation of the Pt-skin structure in O2 produced a FeO surface structure, FeO/Pt(111). This was transformed into a surface Fe structure by mild reduction in H2 (600 K) and into subsurface Fe by further severe reduction (800 K). The transformation of surface Fe (FeO) and subsurface Fe in Pt(111) was reversible in cycled oxidation and reduction treatments. The results demonstrated the controlled preparation of various Fe-Pt surfaces. This can be important for the design of high-performance and low-cost catalysts.