Heat transfer on a vapor bubble rising in superheated liquid is investigated by direct numerical simulation. The vapor–liquid system is described by the one-fluid formulation with the level set method capturing the interface. The proportional-integral-derivative controller is employed to keep the bubble's location fixed and evaluate interfacial forces. The heat transfer performance featured by the Nusselt number is evaluated based on the energy balance. Simulations are carried out for the bubble Reynolds number ranging from 20 to 500 and Morton number from 1.10 × 10−10 to 3.80 × 10−4. The aim of this paper is to shed some light on the effect of bubble deformation and oscillation on interfacial heat transfer. The results show that the front part of the bubble contributes to the majority of the interfacial heat transfer, while the rear part mainly affects the oscillation amplitude of the total heat transfer. The interface stretch during bubble oscillation is considered as a key mechanism in enhancing the instantaneous Nusselt number. The potential flow solution of the averaged Nusselt number is corrected by considering the influence of the aspect ratio. This research provides additional insights into the mechanism of interfacial heat transfer, and the results apply equally to interfacial mass transfer.