The interlayer exchange coupling and the perpendicular magnetoresistance of Fe/Si/Fe systems have been investigated within the fully relativistic screened Korringa-Kohn-Rostoker method and the Kubo-Greenwood equation considering interdiffusion effects, i.e., inhomogeneous Fe-Si alloy formation at the interfaces. It is shown that the experimentally observed strong antiferromagnetic interlayer exchange coupling is caused by the formation of Fe-Si alloys at the interface. Furthermore, our calculations give evidence that the small magnetoresistance, which has been observed experimentally in Fe/Si/Fe trilayers has a similar origin. The results presented here give no evidence for a direct connection between the magnetoresistance and interlayer exchange coupling in Fe/Si/Fe systems.