Fluorine was incorporated into SnO2 nanoparticles from polyvinylidene fluoride (PVdF) by co-milling. The incorporation process was triggered by an oxidative partial decomposition of PVdF due to the abstraction of oxygen atoms, and began soon after milling with a simultaneous decrease in the crystallite size of SnO2 from 56 nm to 19 nm, and increase in the lattice strain by a factor 7. Appearance of D and G Raman peaks indicated that the decomposition of PVdF was accompanied by the formation of nanometric carbon species. Decomposing processes of PVdF were accompanied by the continuous change in the states of F, with a decrease of C-F in PVdF and increase in Sn-F. This indicates the gradual incorporation of F into SnO2, by replacing a part of oxygen in the oxide with fluorine. These serial mechanochemical reaction processes were discussed on the basis of X-ray diffractometry, FT-IR, Raman and UV-Vis diffuse reflectance spectroscopy, transmission electron microscopy, F1s, Sn3d and C1s X-ray photoelectron spectroscopy and Auger electron spectra, as well as magic angle spinning NMR spectroscopy of 19F and 119Sn. The present findings serve as an initial stage of incorporating fluorine into SnO2 via a solvent-free solid-state process, toward the rational fabrication of fluorine doped SnO2 powders.