Light-emitting electrochemical cells (LECs) show high technical potential for display and lighting utilizations owing to the superior properties of solution processability, low operation voltage, and employing inert cathodes. For maximizing the device efficiency, three approaches including development of efficient emissive materials, optimizing the carrier balance, and maximizing the light extraction have been reported. However, most reported works focused on only one of the three optimization approaches. In this work, a combinational approach is demonstrated to optimize the device efficiency of LECs. A sophisticatedly designed yellow complex exhibiting a superior steric hindrance and a good carrier balance is proposed as the emissive material of light-emitting electrochemical cells and thus the external quantum efficiency (EQE) is up to 13.6%. With an improved carrier balance and reduced self-quenching by employing the host-guest strategy, the device EQE can be enhanced to 16.9%. Finally, a diffusive layer embedded between the glass substrate and the indium-tin-oxide layer is utilized to scatter the light trapped in the layered device structure, and consequently, a high EQE of 23.7% can be obtained. Such an EQE is impressive and consequently proves that the proposed combinational approach including adopting efficient emissive materials, optimizing the carrier balance, and maximizing the light extraction is effective in realizing highly efficient LECs.