Improved liquid Li wettability on a solid substrate surface is a necessary component for the research and development of blanket coolants, tritium breeders, and first wall materials for fusion device. A systemic investigation of Li wetting a 316 L SS surface, along with interfacial interactions has been successfully carried out. The results indicate that base vacuum pressure of the vessel, substrate temperature, and surface conditions of the substrate are the main factors that influence Li wetting property. It has been found that poor vacuum (> 10(-1)Pa) along with high impurity content, especially water, can prevent Li wetting due to the formation of a layer of complex Li compounds, such as LiOH, Li3N and Li2CO3. Also, Li wetting can be gradually improved with an increase of substrate temperature, mainly due to a decrease in surface tension of Li droplets. Moreover, Li wetting can be further improved by effective surface conditioning. It has been demonstrated that baking was beneficial in order to release impurity gas by thermal desorption and thereby achieve high vacuum during Li wetting, which resulted in a reduction of > 50 degrees C in Li wetting temperature on the SS substrate. He-GDC and Li coating can further decrease Li wetting temperatures to the Li melting point (similar to 180 degrees C) by avoiding the formation of Li2O at the interfacial surface during Li wetting. This is achieved primarily because these conditioning techniques can effectively remove and isolate the SS surface oxide layer (Cr2O3), respectively, which was verified by the related testing of interfacial interactions between liquid Li and SS. Finally, surface textured structures with trenches similar to mu m in size, are demonstrated to promote Li spreading along the groove direction, driven by capillary forces. These results provide the technical support for liquid Li applications in future fusion reactors.