Contact electrification is about the charge transfer between the surfaces of two materials in a contactseparation process. This effect has been widely utilized in particle separation and energy harvesting, where the charge transfer is preferred to be maximized. However, this effect is always undesirable in some areas such as electronic circuit systems due to the damage from the accumulated electrostatic charges. Herein, we introduced an approach to purposely manipulate the contact electrification process both in polarity and magnitude of the charge transfer through an applied electric field between two materials. Theoretical modeling and the corresponding experiments for controlling the charge transfer between a Pt coated atomic force microscopy tip and Parylene film have been demonstrated. The modulation effect of the electric field on contact electrification is enhanced for a thinner dielectric layer. This work can potentially be utilized to enhance the output performance of energy harvesting devices or nullify contact electric charge transfer in applications where this effect is undesirable. KEYWORDS: Contact electrification, atomic force microscopy, scanning Kelvin probe microscopy, nanogenerators C ontact electrification is a universally existing phenomenon of the charge transfer between surfaces of two materials in a contact-separation process. 1 It has been regarded as detrimental problems in a numbers of situations such as electronic circuits and systems, which thus attract extensive efforts to alleviate this effect. 2 On the other hand, this effect has also been utilized for different purposes such as painting, 3,4 particle separation, 5 and mechanical energy harvesting, 6,7 the last of which uses contact electric charges as electrostatic induction sources to generate electricity from mechanical energy in the form of impact, 8,9 sliding, 10−12 rotation, 13 and so forth. For the sake of better performances in these applications, higher density of charges transferred in the contact electrification process is always favorable. 14,15 Therefore, in all of the studies and applications related to the contact electrification, control of this effect is a critical issue. Previously, the modulation of contact-electric charge density was realized through intrinsic approaches such as material selection 16,17 and surface functionalization 18−20 that directly changes the structure of the two surfaces that are in contact. However, these methodologies are sometimes largely limited by the feasibility of material choices in some applications. So far, there have been few reports about the extrinsic method that can control charge transfer at insulator surfaces within preset materials. Using our recently developed atomic force microscopy (AFM) based in situ triboelectric characterization method, 21 it is possible to investigate extrinsic approaches that can modulate the contact electrification process, which can be potentially utilized to enhance the output performance of energy harvesting devices or nullify the co...