Electric discharge in liquids is an emerging field of research, and is involved into various environmental applications (water purification, fuel reforming, nanomaterial synthesis, etc.). Increasing the treatment efficiency with simultaneous decreasing of the energy consumption are the main goals of today’s research. Here we present an experimental study of nanosecond discharge in distilled water covered by a layer of dielectric material. We demonstrate through this paper that the discharge efficiency can be improved by changing the interface position regarding the anode tip. The efficiency increase is due to the increase of the discharge probability as well as the plasma volume. The understanding of the experimental results is brought and strengthened by simulating the electric field distribution, using Comsol Multiphysics software. Because the dielectric permittivity (ε) is discontinuous at the interface, the electric field is enhanced by a factor that depends on the relative value of ε of the two liquids. The present result is very promising in future: opportunities for potential applications as well as fundamental studies for discharges in liquid.