Turn-on time is a key factor for lighting devices to be of practical application. To decrease the turn-on time value of a deep-red light-emitting electrochemical cells (DR-LECs), two novel approaches based on molecularly engineered ruthenium phenanthroimidazole complexes were introduced. First, we found that with the incorporation of ionic methylpyridinium group to phenanthroimidazole ligand, the turn-on time of the DR-LECs device was dramatically reduced, from 79 to 27 s. By complexation of ruthenium emitter with Ag+, the turn-on time was improved by 85%, and the EQE of DR-device was increased from 0.62 to 0.71%. These results open a new avenue in decreasing the turn-on time without adding ionic electrolytes, leading to an efficient LEC.