Contact electrification (CE) is one of the oldest topics in physics, which has been discussed for more than 2600 years. Recently, an overlapped electron‐cloud (OEC) model was proposed by Wang to explain all types of CE phenomena for general materials in which a deep overlapping of electron clouds belonging to two atoms results in a lowered potential barrier for electron transfer from one to the other by applying a compressive force, which is simply referred to as Wang transition for CE. Here, the degree of electron‐cloud overlap between two atoms is controlled by using tapping mode atomic force microscopy. A temperature difference and electric field are applied between atoms of two surfaces. It is found that electron transfer only occurs when the contact tip and sample interact in the repulsive‐force region, which corresponds to a strong overlap of the electron clouds. Such a fact even preserves if the tip is at a higher temperature than the sample for 120 K. Alternatively, by applying a bias, electron tunneling would occur when the tip is in the attractive‐force region within which normal electron transfer would not occur. These studies solidify the overlapped electron‐cloud model first proposed by Wang. Further, the temperature and bias effects on the CE are explained based on a modified OEC model.