How to avoid the shortage of floatability and non-purpose flotation in marmatite flotation is a big problem. This paper innovatively studies how to reduce these two negative phenomena from the perspective of grinding media. The effects of steel and stainless-steel balls on the flotation performance of copper-activated marmatite were investigated mainly through flotation tests, redox potential measurements, ion concentration tests, and XPS and FT-IR spectrum studies. The flotation results showed that the floatability of copper-activated marmatite remarkably decreased by using the steel ball in the grinding process, but it had a mere influence when stainless-steel medium was used. Redox potential measurements showed that the grinding environment of stainless-steel medium could exhibit a higher oxidizing potential than the steel grinding environment. Results from FTIR, XPS, and ion concentration measurements demonstrated that more ferric ions existed on the copper-activated marmatite surface in the steel grinding environment than that in the stainless-steel environment. Ferric ions could further hinder the activation effect of copper ions on marmatite and result in decreased marmatite flotation. This research could potentially explain the mechanism of ferric ions in the grinding process, and it can be utilized to improve the flotation performance of marmatite ore through selecting suitable grinding media in ball mill operations.