In this article, we report an investigation of laser-initiated ignition of pure iron rods, using optical pyrometry, video observations, and analysis of metallographic cross section of quenched burning liquid on copper plates. When ignition occurs, caused by the melting of metal, the combustion takes place in the liquid. Two distinct superposed phases (L1 and L2) are identified in the liquid, according to the known phase diagram of the iron oxide system. Our observations show that the L1 and L2 phases can be either distinct and immiscible or mixing together. The temperature of the transition at which the mixing occurs is around 2350 K. Two mechanisms are proposed to explain the mixing occurring at high temperature: the spontaneous emulsification resulting from a strong decrease of the interfacial tension between L1 and L2 and the reduction of the miscibility gap between them at high temperature. Based on the experimental data of the evolution of the temperature and the video observation of the melt for different ignition conditions, we provide a complete description of the combustion process of iron induced by laser. Eventually, an extrapolation of the iron-oxygen phase diagram, to temperatures higher than 2000 K, is proposed.