This work describes recent research into the mechanisms behind tribocharging and the influence of triboemission. The term tribocharging is a type of contact-induced electrification and refers to the transfer of charge between rubbing components. The term triboemission, on the other hand, refers to emission of electrons, ions and photons generated when surfaces are rubbed together. The understanding of tribocharging is of wide interest for several industrial applications and in particular the combination of tribocharging and triboemission may be important in lubricated contacts in the formation of boundary lubricant films. We report the use of a unique vacuum measurement system that enables to measure surface charge variations while simultaneously recording triboemission events during the sliding of a diamond tip on silica specimens. Results show for the first time that tribocharging and triboemission behavior are linked and depend on the surface wear. The contribution of contact-induced electrification to the charging of the surface is then described by means of density functional theory (DFT). Results give insight into the transfer of charge from the SiO₂ amorphous surface (silica) to the C(111) surface (diamond ) and into the variation of charging during simulated sliding contact.