The exceptional physical, chemical, electric, and mechanical properties of ceramics, glass and diamond film make them receive much attention in high-tech industry. Although the electrochemical discharge machining (ECDM) can be used to process those materials, most ECDM are used for machining micro-holes and wire cutting. However, the application on the polishing aspect is still scarce in the literature. In this study, a high-precision dynamic electrical pitting tester with the electrolyte of KOH is employed to investigate the behavior of static electrochemical discharge in terms of supply voltage and gap distance between the steel ball and the diamond film. Furthermore, its machining characteristics are also analyzed. According to the current waveform, the I-V curve is plotted. Results show that the current value of glass is higher than that of diamond film and acrylic. This indicates that the glass is easily to be ionized. According to the observation on the surface of machined diamond film by using SEM, the machined status can be divided into four regimes. In the first regime, the supply voltage is less than 100V where the machined mark on the diamond film cannot be found. Hence, it is called non-machined regime. In the second regime, the supply voltage is in the range between 100 and 107V, where only very slight damage can be observed on the diamond film. Hence, it is called the fine machined regime. In the third regime, the supply voltage is in the range between 107 and 110V, where the machined status on the diamond film is unstable. Hence, it is called the transition regime. In the fourth regime, the supply voltage is larger than 110V, where the machined damage is very heavy. Hence, it is called the rough machined regime. At the supply voltage 105V with the gap less than 80£gm, the annular shape of the machined damage on the surface of the diamond film can be observed. However, when the gap is in the range between 80£gm and 95£gm, the annular shape of the machined damage disappears, but there is still slight damage at the asperity of the diamond film. When the gap is larger than 95£gm, the machined damage is invisible. Hence, the critical gap is defined as 95£gm for the supply voltage of 105V. At the supply voltage of 105V, the gap of 90£gm, and the machining time of 10 min, only the asperity of diamond film shows machined mark, but the surface is flatter. Therefore, it is possible to conduct the fine machining process by using ECDM on diamond film.