Electrochemical reduction of solid GeO2 has been investigated in the mixed CaCl2-NaCl melt at 1023K for developing a more efficient process for preparation of Ge. Cyclic voltammetry and potentiostatic electrolysis were applied to study the GeO2-loaded metallic cavity electrode. In addition, porous GeO2 pellets were reduced by potentiostatic and constant cell voltage electrolysis with a graphite anode, and the electrolysis products were analyzed by powder X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray spectrometry, focusing on understanding the reduction mechanism and the impact of electrode potential on the product purity. It was found that the reduction of GeO2 to Ge occurred at a potential of about -0.50V (vs. Ag/Ag+), but generating various calcium germanates simultaneously, whose reduction was a little more difficult and needed a potential more negative than -1.00V. However, if the cathode potential exceeded -1.60V, Ca (or Na) - Ge intermetallic compounds might form. These results gave an appropriate potential range between -1.10 and -1.40V for the production of pure germanium. Rapid electrolysis of GeO2 to pure Ge has been realized at a cell voltage of 2.5V with a current efficiency of about 92%.