Well-arrayed submicrometer holes were formed when a tetrahydrofuran solution of styrene-maleic anhydride alternating copolymer (SMA) containing water and hydrochloric acid was spin-cast onto Si wafer substrates. The heres in these films on solid substrates were interpreted as the traces of water droplets emulsified by hydrolyzed SMA during evaporation process of spin-casting. Atomic force microscopy (AFM) also revealed traces of emulsified water droplets and their fusion actions in a non-spin-casting process. Experimental evidences showed that the holes can be used as templates to direct the growth of gold particles when gold is deposited from its vapor.