A member provided with a composite coating excellent in the resistances to corrosion and molten metals, having a high resistance to the peeling or breakage of the coating, and also excellent in the resistances to heat and thermal impact. The composite coating is formed on the surface of a steel material by first forming thereon a spray coating of metals (including alloys), oxide and non-oxide ceramics, and cermets comprising these metals and ceramics as an undercoat and then forming thereon a vitreous coating as a topcoat. The composite coating is provided with an oxide layer on the surface (on the side of the vitreous coating) of the spray coating as the undercoat, thus improving tight adhesion of the undercoat to the vitreous coating as the topcoat in virtue of the moderate unevennesses and pores of the oxide layer.