Mössbauer spectroscopy, DSC and magnetic measurements have been used to study the influence of B and P on structural; magnetic properties and thermal stability of cast iron based alloys. Results reveal that addition of B and P affects appreciably: (1) the crystallization temperature and supercooled liquid region ranging between 690–781 and 53–81 K respectively; (2) the spin texture, disorder and (3) the obtained magnetization parameters. Coercive field values range between 10.09 and 16.37 A/m, with lowest value of 10.09 A/m obtained for Ci87.82B12.17. Saturation induction (Bs) values vary between 1.32 and 1.85 T. Highest Bs value of 1.85 T is obtained for the Ci95.65B4.32 alloy which is at the edge of glass forming ability, with only 4.32 at.% of boron was added to the cast iron composition. Losses (at 50 Hz and 0.32 kA/m) for the studied samples range between 0.43 and 0.82 W/kg. Lowest losses of 0.43 W/kg was obtained for the Ci91.3P4.35B4.35 alloy. Phosphorous and boron additions, helps in the bulk glass forming ability, suggesting perspective applications of these cheap cast iron based soft magnetic alloys as a substitute of the conventional materials.