An investigation has been made of the electrostatic charge produced in vacuum on several inorganic insulators when they are put into rolling contact with nickel, platinum, and copper surfaces. The primary role of relative motion is to increase the area on the insulator that ultimately undergoes contact, thereby increasing the total charge separated. With quartz, all evidence favors electron transfer which occurs because the nonconductor has a higher effective work function than the metal. Field emission‐induced back leakage of electrons during separation of the charged surfaces is considered to reduce the charge originally separated to that actually measured. Little difference is seen between the charging properties of quartz cleaned chemically in room air and quartz subsequently outgassed at 700°Cin vacuobetter than 10−8mm Hg. No difference in electron affinity is found between fused and monocrystalline quartz. No evidence directly supporting electron transfer is found for the other insulators tested, synthetic single crystals of Al2O3, MgO, NaCl, KCl, KBr, and KI; and the possibility of ion transfer is considered. All charge against nickel much less vigorously and less reproducibly than does quartz. The alkali halides and MgO which contains excess Mg or O as a bulk impurity charge positively, while stoichiometric MgO charges negatively. With Al2O3, there is a strong dependence of charge density on crystallographic orientation. Alteration of charging properties by surface and/or bulk conduction is found to be negligible for all insulators tested, within the reproducibility of the charging measurements.