In microelectrical discharge machining (micro-EDM) milling process, due to the unavoidability of electrode wear, selection of electrode with high electrical erosion resistance and accurate electrode compensation is entitled to be conducted to ensure high precision and high quality. The RVWR is used as criterion for electrode wear characteristics and is fundamental to achieve accurate electrode compensation; however, it is hardly measured accurately with conventional methods. In this paper, firstly, the error of RVWR measured by conventional measurement method is analyzed. Thereafter, for accurately measuring RVWR, a new measurement method is proposed based on electrical debris composition analysis. The RVWR of widely used tungsten, molybdenum, and copper electrode in machining different materials is measured, respectively, and the optimum electrode is selected based on the measuring results. Finally, microgrooves on different materials are machined with tungsten electrode, and the experiment results show that the microstructures have good bottom surface profiles, which indicates that the proposed method is effective to precisely measure the RVWR and guarantee accurate electrode compensation in micro-EDM process.