The information on the interactions between coke and pitch is of great value for the aluminum industry. This information can help choose the suitable coke and pitch pairs as well as the appropriate mixing parameters to be used during the production of anodes. In this study, the interaction mechanisms of pitch and coke at the mixing stage were studied by a sessile-drop test using two coal-tar pitches as the liquid and three petroleum cokes as the substrate. The results showed that the coke–pitch interactions are related to both pitch and coke chemical compositions. The contact angle of different coke–pitch systems decreased with increasing time and temperature. At high temperatures, decreasing the pitch viscosity facilitated the spreading of pitch and its penetration into the coke bed. The chemical behavior of petroleum cokes and coal tar pitches were studied using the FT-IR spectroscopy and XPS. The results showed that the wettability behavior of cokes by pitches depends on their physical properties as well as the presence of surface functional groups of coke and pitch which can form chemical bonds.