Molecular doping of inorganic semiconductors is a rising topic in the field of organic/inorganic hybrid electronics. However, it is difficult to find dopant molecules which simultaneously exhibit strong reducibility and stability in ambient atmosphere, which are needed for n‐type doping of oxide semiconductors. Herein, successful n‐type doping of SnO2 is demonstrated by a simple, air‐robust, and cost‐effective triphenylphosphine oxide molecule. Strikingly, it is discovered that electrons are transferred from the R3P+O−σ‐bond to the peripheral tin atoms other than the directly interacted ones at the surface. That means those electrons are delocalized. The course is verified by multi‐photophysical characterizations. This doping effect accounts for the enhancement of conductivity and the decline of work function of SnO2, which enlarges the built‐in field from 0.01 to 0.07 eV and decreases the energy barrier from 0.55 to 0