Determination of Mn and Ni in High carbon ferrochrome is not elaborated in any chemical analysis methods of Indian or International standards. It becomes a challenge for stainless steel makers to produce SS with restricted Mn and Ni content in certain grades. Fusion of High carbon ferrochrome in the nickel crucible interfere the determination Mn in presence of Cr and Ni, again fusion of High carbon ferrochrome in iron crucible landed similar interference due to excess Fe. Similar interferences were also noticed during Ni estimation in fusion methods. A combination of tri-acids dissolution in a Teflon beaker with removal of Cr as chromyl chloride, followed by Mn oxidation with ammonium peroxodisulfate in presence of silver nitrate and arsenite titration could furnish results with repeatability in comparison to CRM standards. As the dissolution rate is slow hence this tri-acid dissolution method is time consuming. Trial estimation by fusing in Zr-crucible, with removal of Cr eliminate Ni interference and fast determination of Mn in High carbon ferrochrome in permanganate - arsenite titration with repeatability. Similarly Ni estimation done by fusing the High carbon ferrochrome in Zr-crucible followed precipitation with DMG and filtration – ignition. XRF instrument calibrated and standardised with local High carbon ferrochrome standards developed in-house by chemical analysis and validation of results of analysis, demonstrated by accuracy, precision and LOD on inter-lab basis, which augments the novelty of the work. The results helps SMS operation to balance the charge and optimise ferroalloy additions to control the chemistry of finished steel as per desired Mn and Ni.