Silicon determination on stainless steel alloys via inductively coupled plasma optical emission spectrometry (ICP‐OES) is a topic not yet fully explored in the literature. In the extreme acidic conditions necessary for the dissolution of these samples, phenomena such as polymerization and aggregation of silicon particles may strongly affect the result. A low recovery may be expected if the analytical steps are not properly conducted. Herein, different experimental layouts with certified reference materials are devised to demonstrate the weak spots of this technique and to provide a clear understanding on how to cope with this issue.