Fe-Si alloys are excellent soft magnetic materials: with increasing Si content and a peak at 6.5% Si they present almost zero magnetostriction, increasing electrical resistance and permeability, low Eddy current losses and low hysteresis losses. Silicon steels contain usually up to 3.5% Si because a higher content makes the material extremely brittle and very difficult to cold-roll. The reason of this behavior has been generally attributed to structural ordering (132 and D0(3)). Thermomechanical processing of high silicon steel appears to be possible whenever special conditions of temperature and rolling passes are maintained in order to avoid embrittlement. Alloys with Si between 6.4 and 10.3 at.% were produced on a laboratory scale to investigate the effect of order-disorder phenomena on workability. (57)Mossbauer spectroscopy was used to study the effect of thermomechanical cycles on the ordering. Compression tests (at high strain rate) were carried out to study the deformation behavior and the effect of time delay between hot and cold rolling on mechanical properties. An increase of the deformation stress is observed between the deformation steps, which is increasing with higher Si-content and probably caused by an ordering phenomenon. Hot dipping and diffusion annealing is an alternative production route to obtain high silicon contents without rolling. Additional surface alloying with Si and Al is achieved on a normal steel substrate (low Si) by hot dipping in a hypereutectic Al-Si-bath. To obtain a sufficient amount of Al and Si in solid solution over the thickness, diffusion annealing is performed after hot dipping. Characterization of the deposited layer and of the diffusion gradients was performed, the magnetic properties are comparable with the best commercial values of oriented electrical steel.