Ball-milled Ni-Al powder compacts have been synthesized by the heat of molten cast iron and have been coated on cast iron. The effects of the ball-milling time on the microstructure of the intermetallic coatings have been investigated. The experimental results showed that the ball-milled Ni-Al powder compacts were completely reacted and were successfully coated on the cast iron without re-melting the substrate. Densification of the coating layers was enhanced by increasing the ball-milling time. This might be attributed to the fact that the heat released during the intermetallic reaction was dispersed over a prolonged reaction time by the ball-milling of the elemental powders.