Exchange coupling observed recently in Fe/ Fe3O4 (001) junctions shows comparable intensity to that in Co/Ru/Co trilayers, and has potential applicability to spintronics devices. To clarify the mechanism of the exchange coupling, electronic and magnetic states of Fe/ Fe3O4 junctions are calculated in the first principles method by assuming four junction structures of bcc Fe and Fe3O4 layers. It is shown that the local moments of bcc Fe atoms at the interface increase, but those of Fe ions at the interface of Fe3O4 layer decrease. The total energy of the junctions is plotted as a function of distance between Fe and Fe3O4 layers. Calculated results of the coupling energy between Fe and Fe3O4 layers, however, are larger than experimental ones by two orders of magnitude, and they correspond to inter-atomic exchange interactions at the interface. In order to explain the experimental results, we propose a mechanism of exchange coupling mediated by impurity-like states of interfacial Fe atoms which possess reversed magnetic moments in bcc Fe layer. Frustration effects in exchange coupling between Fe and Fe3O4 layers are also discussed.