This work studied the morphology of the interfacial layers formed on the substrates with different surface roughness in a bath containing 0.3 wt% Al at 460 °C. The immersion time was set to 8 s, 60 s, 180 s, 300 s, 600 s, 1200 s, and 1800 s, respectively. The as-prepared samples were characterized by the 3D laser scanning microscope, the grazing incident X-ray diffraction, the field emission scanning electron microscope, the inductively-coupled plasma mass spectrometry, the transmission electron microscope, and the electron back-scattered diffraction. The results showed that the morphology and the crystal orientation of the interfacial layer varied significantly with the change of surface roughness. A thick, compact mono-orientated interfacial layer was formed on the substrate with Ra = 0.031 μm and no out-burst was observed even for an 1800 s immersion. However, the thinner, discrete interfacial layers with the randomly-distributed orientation were formed on the substrate with Ra = 0.455 μm and 0.112 μm and the out-burst appeared for less than 60 s immersion. The mechanism of the out-burst formation also changed with the surface roughness. For Ra = 0.455 μm, the out-burst emerged along the grooves, but it only appeared in certain areas for Ra = 0.112 μm.