Pt nanofibers have been prepared with a redox reaction occurring spacio-selectively at the liquid-liquid interface between a highly hydrophobic ionic liquid (IL) and water (W), which has been utilized as two dimensional reaction field. The preparation is conducted based on the concept of the coupling between ion transfer (IT) and electron transfer (ET) across the IL|W interface, which previously enabled direct formation of dendritic Au nanofibers at the IL|W interface (Chem. Commun., 2015, 51, 13638). The successful preparation of Pt nanofibers has manifested the generality of the IL|W interface method for the formation of metal nanofibers. Electrochemical measurements at the IL|W interface have confirmed that IT of PtCl4 2from W to IL is actually coupled with ET between PtCl4 2initially dissolved in W and decamethylferrocene in IL, leading to the spontaneous formation of Pt nanofibers at the IL|W interface. Herein, IT of PtCl4 2ions from W to IL not merely neutralizes the excess charges generated in each liquid phase by ET, but also provides PtCl4 2into IL as reactants for the growth of Pt nanofibers that takes place at the IL side of the IL|W interface. The electrocatalytic activity of the Pt nanofibers in oxygen reduction reaction (ORR) has also been evaluated.