Abstract: Due the limited supply of fossil fuels and environmental degradation arising from flue gas emissions,it is imperative to discover clean and sustainable energy, and to develop effective and green energy storage devices.Conventional lithium ion batteries cannot meet the requirements of future large scale electrical applications such as electrical automobiles which need higher energy density. We present here an overview of our recent work,beginning with an introduction to the concept and principle of hybrid electrolytes,and followed by a detailed discussion of the design and electrochemical performance of hybrid electrolyte-based post-lithium batteries such as Li-Cu and Li-air batteries.The hybrid electrolyte technology is considered to be a promising method to develop electrochemical high energy storage devices.