By combining contact-mode atomic force microscopy (AFM) and scanning Kevin probe microscopy (SKPM), we demonstrated an in situ method for quantitative characterization of the triboelectrification process at the nanoscale. We systematically characterized the triboelectric charge distribution, multifriction effect on charge transfer, as well as subsequent charge diffusion on the dielectric surface: (i) the SiO2 surface can be either positively or negatively charged through triboelectric process using Si-based AFM probes with and without Pt coating, respectively; (ii) the triboelectric charges accumulated from multifriction and eventually reached to saturated concentrations of (-150 ± 8) μC/m(2) and (105 ± 6) μC/m(2), respectively; (iii) the charge diffusion coefficients on SiO2 surface were measured to be (1.10 ± 0.03) × 10(-15) m(2)/s for the positive charge and (0.19 ± 0.01) × 10(-15) m(2)/s for the negative charges. These quantifications will facilitate a fundamental understanding about the triboelectric and de-electrification process, which is important for designing high performance triboelectric nanogenerators. In addition, we demonstrated a technique for nanopatterning of surface charges without assistance of external electric field, which has a promising potential application for directed self-assembly of charged nanostructures for nanoelectronic devices.