Electrical discharge machining (EDM) is a non-traditional process, which can cut materials with a high melting point, high hardness, high strength, and low brittleness. However, the kerosene (dielectric of EDM) produces aerosols and toxic gases at high temperatures, which seriously affect the health of operators and air quality. This means that it is not conducive to the green manufacturing and sustainable development of EDM. In this study, thereafter, sunflower seed oil (SSO) and kerosene were used as dielectrics of EDM for machine SKD11, and the machining performance of the two dielectrics under different current, duty ratio, pulse duration and electrodes were comparatively analyzed, such as material remove rate (MRR), surface roughness (Ra), energy efficiency per volume (EEV) and exhaust emissions characteristics (EEC). This investigation found that the minimum value of EEV in SSO was 0.3879 kJ/mm3, which was about 25% lower than the minimum value of 0.4849 kJ/mm3 in kerosene. The emission rate of Cu electrode in SSO was 62.017 µg/min, which was lower than that in 78.857 µg/min, decreasing by about 21.36%, in kerosene. In addition, a super depth of field optical micro-scope was subsequently used in the experiments to observe the diameter of the debris. The results indicated that SSO has a larger proportion of debris of more than 35 µm in diameter. Therefore, SSO can be adopted as a substitute for kerosene dielectric to improve the sustainability of electrical discharge machining and realize green manufacturing.