In this paper, the best laser powder bed fusion (L-PBF) printing conditions for FeSi steels with two different Si content (3.0% and 6.5%) are defined. Results show very strict processing window parameters, following a lack of fusion porosity at low specific energy values and keyhole porosity in correspondence with high specific energy values. The obtained microstructure consists of grains with epitaxial growth starting from the grains already solidified in the underling layer. This allows the continuous growth of the columnar grains, directed parallel to the built direction of the component. The magnetic behaviour of FeSi6.5 samples, although the performances found do not still fully reach those of the best commercial electrical steels (used to manufacture magnetic cores of electrical machines and other similar magnetic components), appears to be quite promising. An improvement of the printing process to obtain thin sheets with increased Si content, less than 0.5 mm thick, with accurate geometry and robust structures, can result to an interesting technology for specific application where complex geometries and sophisticated shapes are required, avoiding mechanical machining processes for electrical steel with high silicon content.