The synthesis of the high-pressure ε phase of iron, which has not been observed under a conventional shock compression, was attained using a femtosecond laser. The lower pressure and temperature α phase (bcc) transforms to the γ phase (fcc) at higher temperatures and to the ε phase (hcp) at higher pressures. A shock induced α to ε phase transition in iron is one of the most famous transitions under high pressure. The induced high-pressure ε phase by a conventional shock loading returns to the α phase and it is not quenched after the shock release because this transition is considered to be diffusionless. Crystalline structures in a recovered iron sample after the femtosecond laser (800 nm, 120 fs, 1014 W/cm2) irradiation were determined using the electron diffraction and the synchrotron X-ray diffraction methods. These results show the existence of the ε phase and the fcc structure in the recovered iron. The femtosecond laser-driven shock wave may have the potential to synthesis high-pressure phases of other materials that has not been done using the conventional shock wave.