Highly efficient exciplex emission in solid-state light-emitting electrochemical cells (LECs) was achieved by mixing two ionic fluorescent emitters with opposite bipolarity. A triarylamine derivative as a hole-transport material (HTM) and a 1,3,5-triazine derivative as an electron-transport material (ETM) were selected due to their superior carrier mobilities. The ionic character of HTM and ETM was achieved by chemically attaching three pendant methylimidazolium groups as peripheries, rendering them amenable to LEC applications. Strong exciplex green emission can be observed either from photoluminescence in solid states or electroluminescence in LEC devices when HTM and ETM are mixed. By optimizing the mixing ratio, the external quantum efficiency and power efficiency can be achieved up to 3.04% and 10.29 lm W−1, respectively. These results are among the highest reported for fluorescent LECs.