Electrically controlled droplet manipulation is attractive for lots of applications ranging from material synthesis and drug delivery. However, the present techniques using bulky and expensive power supplies to generate high‐voltage electrical signals are easy to cause electrode electrolysis, bubble formation in buffer solution, and are incapable for point‐of‐care testing. Herein, a novel and portable electrical method for self‐powered emulsion droplet core coalescence and release based on triboelectric nanogenerator (TENG) is presented. The electrical signal with a 2.25 kV open‐voltage and a 35 µA short‐circuit current can be conveniently generated via frictional electrification effect, and the harmful electrochemical reaction in solutions can be avoided. The high transient pulse voltage and stable sinusoidal signal between two electrodes in microfluidic device can generate a strong electric field, which causes apparent Maxwell electrical stresses at droplet interfaces and subsequently promotes the core coalescence and release of double‐emulsions. By adjusting the voltage magnitude, the core coalescence and release behaviors of double‐emulsion droplets can be controllably achieved, followed by the synthesis copper‐based metal–organic framework (Cu‐MOF) nanoparticles. Thus, this portable, effective and self‐powered droplet manipulation technique can be attractive for those droplet‐based applications.