Optimization of 3D printing parameters was studied for the difficult to print, brittle Fe-6.5 wt%Si, applying powder bed fusion (PBF) technology. Printing orientation, volumetric energy density (VED), built plate (BP) temperature, as deposition parameters and the influence of post-deposition heat treatment (HT), were investigated. The optimal parameters were established based on the EBSD figures of samples deposited in different orientations, optical microscopy images, CT measurements, DC hysteresis curves, complex permeability spectra, and XRD patterns.