The nanofriction properties of hexagonal boron nitride (h-BN) are vital for its application as a substrate for graphene devices and solid lubricants in micro- and nano-electromechanical devices. In this work, the nanofriction characteristics of h-BN on Si/SiO2 substrates with a bias voltage are explored using a conductive atomic force microscopy (AFM) tip sliding on the h-BN surface under different substrate bias voltages. The results show that the nanofriction on h-BN increases with an increase in the applied bias difference (Vt–s) between the conductive tip and the substrate. The nanofriction under negative Vt–s is larger than that under positive Vt–s. The variation in nanofriction is relevant to the electrostatic interaction caused by the charging effect. The electrostatic force between opposite charges localized on the conductive tip and at the SiO2/Si interface increases with an increase in Vt–s. Owing to the characteristics of p-type silicon, a positive Vt–s will first cause depletion of majority carriers, which results in a difference of nanofriction under positive and negative Vt–s. Our findings provide an approach for manipulating the nanofriction of 2D insulating material surfaces through an applied electric field, and are helpful for designing a substrate for graphene devices.