The invention relates to a process and a device of forming a multilayer insulating thin film on an inner wall of a glass container. The device includes a machine base, a gas transportation pipeline, a microwave sealing cover, an antenna, a mode convertor, a tuner, a waveguide tube and a pulse microwave generating source. The invention also provides a process corresponding to the device, comprising following steps: (1) vacuumizing the microwave sealing cover and feeding oxygen to the microwave sealing cover through the gas transportation pipeline; (2) introducing a high-power pulse microwave generated from the pulse microwave generating source to the mode convertor through the waveguide tube, tuning the high-power pulse microwave by the tuner, and enabling the high-power pulse microwave to pass through the antenna and uniformly enter into the interior of the vacuum glass container; (3) feeding various special gases successively into the vacuum glass container and ionizing the special gases to generate compact and uniform oxide thin films, wherein the thin films in different nano-scale thicknesses are alternatedly deposited onto the inner wall of the glass container. With the process and the device, the inner wall of a glass container in complex structure can be coated by the thin film, thereby increasing the service life of the product and the deposition efficiency, reducing production cost and enhancing film layer adhesive force and uniformity.