Fouling is one of the common problems in heat-transfer applications, resulting in higher fouling resistance, and lower heat-transfer coefficient. This paper introduces the design and fabrication of an Fe–Al coating with micro/nanostructures on low-carbon steel by electrical discharge coating (EDC) technology to improve the antifouling property. The Fe–Al coating with micro/nanostructures is characterized by a large number of micro/nanostructures and superior anti-fouling property, which is attributed to its hydrophobic surface. The antifouling property, fouling induction period and contact angle of the Fe–Al coating with micro/nanostructures increase with the increasing gap voltage. Compared with the polished surface of low-carbon steel, the Fe–Al coating with micro/nanostructures extends the induction period from 214 to 1350 min, with a heat flux of 98 kW·m−2. After 50 adhesion tests, the contact angle of the Fe–Al coating with micro/nanostructures decreases from 6.81% to 27.52%, which indicates that the Fe–Al coating with micro/nanostructures is durable and suitable for industrial applications.