By developing low‐refractive‐index organic hole‐ and electron‐transport materials enabling the efficiency (cd/A/CIEy) of a top‐emission blue fluorescent OLED to be increased by 12% and 11%, respectively, the blue fluorescent OLED has achieved the ultra‐high efficiency over 250 ca/A/CIEy without the need of a special light‐outcoupling structure or film.