Systematic atomistic simulations of homo-and hetero-phase boundaries have been carried out to quantify interphase boundary energies in iron including ¤-phase and £-phase grain boundaries and ¤/£, ¤/liquid and £/liquid interfaces. Due to structural mismatch between body centered cubic (BCC) and face centered cubic (FCC) structures of the ¤ and £ phases, the minimum interface energy of the ¤/£ interface is as high as 0.41 J/m 2 , much higher than the minimum interface energies of the ¤/¤ and £/£ homo-phase interfaces, which are zero, suggesting that the high interface energy is one of the key factors that lead to the massive-like phase transformation from the ¤ phase to the £ phase observed by in situ radiography. Although the minimum ¤/£ interface energy is not significantly higher than the ¤/liquid interface energy that determines the ¤ nucleation upon solidification, it is yet high enough for the small entropy change upon the phase transformation to inhibit £ nucleation at a given critical radius until more than one orders of magnitude higher undercooling is achieved according to the classical theory of homogeneous nucleation.