Silane derivatives with wide energy gap (≈3.5 eV) containing different electron‐withdrawing groups of quinoline and naphthyridine are synthesized and used as the electron transporting materials. The different electron transporting and hole/exciton blocking properties of the silane derivatives are investigated via multilayered structure of organic electrophosphorescent devices by using fac‐tris(2‐phenylpyridine)iridium (Ir(ppy)3) as the phosphorescent emitter. 15.4% of maximum external quantum efficiency (EQE) corresponding to 56.2 cd A−1 of maximum current efficiency is obtained with a maximum power efficiency of 58.9 lm W−1 by employing di‐(4‐(1,8‐naphthyridin‐2‐yl)phenyl)diphenylsilane (DNPS) as the electron transporting material, combining with 2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline as the hole blocking layer, which is higher than the performance of conventional Alq3 device. When changing naphthyridine of DNPS to the electron‐withdrawing group of quinoline (di‐(4‐(isoquinolin‐4‐yl)phenyl)diphenylsilane), only 11.4% of maximum EQE with 41.4 cd A−1 of maximum current efficiency and 32.5 lm W−1 of a maximum power efficiency is obtained. These indicate that the electron transporting ability increases while the electron‐withdrawing group changes from quinoline to naphthyridine, which is also consistent with the calculated reorganization energy.