Iron nanoparticles are highly desirable for their potential applications in magnetic and catalytic industry. However, their shape-controlled fabrication is still an important challenge. Here we successfully synthesized icosahedral face-centered cubic (fcc) Fe nanoparticles with size of 5-13 nm by a specifically designed thermodynamic governed synthetic route, which is facile but highly efficient and reproducible. With the aberration-corrected transmission electron microscopy (TEM), the unique icosahedral structure's pseudo-2-fold, 3-fold, and pseudo-5-fold axes were directly observed for the first time and verified by computer simulation, which reveals that nanoparticles' orientations have a large impact on HRTEM images at ultrahigh resolution. It is expected that as-synthesized Fe nanoparticles with sharp corners and edges would be beneficial for tailoring chemical and physical properties at the nanoscale.