The electrochemical water splitting technology, a cornerstone for the production of “green hydrogen”, holds paramount significance in the global pursuit of carbon neutrality. Steel‐based electrocatalysts, when judiciously designed at the mesoscale, emerge as pivotal players in the quest for cost‐effective and highly active catalysts for industrial‐scale deployment. This domain has witnessed remarkable progress in recent times, prompting this review to offer a holistic overview of the design and synthesis methodologies for steel‐based electrocatalysts. The focus of this review lies in three primary aspects: the intricate phase transition design of the exterior layer, the strategic manipulation of 3D steel‐based substrate architectures, and the ingenious coupling of multifarious heterointerfaces. These strategies collectively contribute to the enhancement of catalytic performance. Concluding the discussion, the key insights are briefly summarized and delved into the challenges and prospects surrounding the advancement of steel‐based electrocatalysts for sustainable, large‐scale hydrogen production. Against the strategic backdrop of integrating computational chemistry, paired electrocatalysis, and industrial‐grade high‐current direct electrolysis of seawater, a roadmap is envisioned that aims to overcome existing barriers and propel the field toward new horizons.