The invention relates to a device and a method for on-orbit monitoring of charging of a satellite material surface, belonging to the technical field of space application. The device comprises an electron gun, a non-contact potentiometer probe, a three-dimensional transmission mechanism, a non-contact surface potentiometer, an electron beam current density measuring system, a monitoring electrode,a supporting structure, a first electromagnetic valve, a second electromagnetic valve, a diffusion pump, a third electromagnetic valve, a vacuum box, a mechanical pump, a vacuum penetrating wall, a measurement circuit interface and a measurement circuit. The test method comprises the steps as follows: sending an electron to a sample for monitoring the electrode surface under a vacuum condition, adjusting the position of the non-contact potentiometer probe through the three-dimensional transmission mechanism, recording charging potential Vsurface on the sample surface, measuring leakage current I through the measurement circuit, and finally obtaining a proportional relation coefficient K by known sample resistance rho according to the formula that Vsurface is proportional to KrhoI. According to the invention, the on-orbit surface charging condition of the satellite material is inverted by monitoring the leakage current of the sample in a space environment, and the device and the methodhas the advantage of simple physical structure and is easy to carry in space.