Nanosecond laser ablated metallic surfaces showed initial super-hydrophilicity, and then experienced gradual wettability conversion to super-hydrophobicity with the increase of exposing time to ambient air. Due to the presence of hierarchical structures and change of surface chemistry, the laser-induced Inconel alloy surfaces showed a stable apparent contact angle beyond 150° over 30-day air exposure. The wetting states were proposed to elucidate the initial super-hydrophilicity and the final super-hydrophobicity. The basic fundaments behind the wettability conversion was explored by analyzing surface chemistry using X-ray photoelectron spectroscopy (XPS). The results indicated that the origins of super-hydrophobicity were identified as the increase of carbon content and the dominance of C–C(H) functional group. The C–C(H) bond with excellent nonpolarity derived from the chemisorbed airborne hydrocarbons, which resulted in dramatic reduction of surface-free-energy. This study confirmed that the surface chemistry is not the only factor to determine surface super-hydrophobicity. The laser-induced super-hydrophobicity was attributed to the synergistic effect of surface topography and surface chemical compositions. In this work, the corresponding chemical reaction was particularly described to discuss how the airborne hydrocarbons were attached onto the laser ablated surfaces, which reveals the generation mechanism of air-exposed super-hydrophobic surfaces.