In this work, Fe and Si powders were used to fabricate 6.5% Si silicon steel. The mixing powder was rolled into strip and then treated at 900°C in Ar. Sn was added into the mixing powder to investigate the effect of Sn on the sintering. The density, composition, and structure were examined. The results show that Fe almost does not react with Si at 900°C. But with the addition of Sn, Fe reacts with Si to produce Fe3Si at 900°C. Increasing the amount of Sn accelerates this reaction. When the amount of Sn addition is excessive, there will leave many pores in the alloy because the reaction rate is too fast to shrink. The proper amount of Sn addition can decrease the sintering temperature and shorten the sintering time.