Solid-state LEC exhibits benefits of the simple structure, easy fabrication procedure, and compatibility with air-stable electrodes. Even with the low cost and easy accessibility, organic small molecule ions are not well known for their excellent electroluminescence in LECs. In this design strategy, we have chosen electron-rich triphenylamine and coupled it with thenil imidazole and phenanthroimidazole from both sides with an alkyl chain substitution at N1 position of the imidazole group to construct active material for non-doped LECs. Detailed systematic investigations on optical, electrochemical, thermal, and electroluminescence properties were carried out. For the fabrication of white LECs for lighting applications, the lack of excellent blue LECs has remained a formidable challenge. Herein, our novel ionic small molecule emitters featured bright blue emissions at 479 and 458 nm with the Commission Internationale de I'Eclairage CIE coordinates (0.20, 0.24) and (0.19, 0.22), respectively. It is a remarkable achievement that without a host or extra ions our devices generated eminent blue emissions with a maximum luminance of 899 and 1073 cd m−2 and peak current efficiencies of 1.97 and 2.27 cd A−1. This shows the potential for LECs as low-cost light sources and offers great promise for devices that utilize specifically developed ionic SMs.