Industrially, the silicon requirement of liquid steel is often met with ferrosilicon (FeSi) instead of high‐purity silicon addition. FeSi, a silicon‐rich alloy, contains impurities typically inherited from its manufacturing stage. Therefore, FeSi addition results in the formation of complex inclusions in the liquid steel. Herein, a detailed inclusion characterization of the samples obtained from the melting experiments for a wide range of silicon concentrations has been carried out to examine the effect of FeSi impurities. Pure silica inclusions evolve to silica‐ and/or alumina‐based Si–Al–(Ti)–O–(TiN) complex inclusions with the increasing addition of FeSi to the steel melt. Reduction of silica by aluminum or titanium, the presence of titanium in the steel melt, and/or TiN inclusions formed at the periphery of oxide inclusions restrict the growth of oxide inclusions, resulting in small‐sized (average) oxide inclusions. The underlying mechanism of such complex (Si–Al–Ti–O–N)‐based inclusions has been explained with the aid of microstructural characterization and thermodynamic calculations. Moreover, the steel–crucible (alumina) interface has also been investigated for inclusion deposits and crucible–steel interaction.