Eu3+‐activated red‐emitting inorganic phosphors have been favored highly for their classical 5D0→7FJ (J = 0, 1, 2, 3, 4) emissions. However, the fatal drawbacks of poor luminous efficacy and weak 5D0→7F4 transition persist, resulting in the ongoing challenge of achieving far‐red emission. This research reports series of highly efficient far‐red phosphors LnTeBO5 (Ln = La3+, Y3+, Gd3+):Eu3+ with anomalously strong 5D0→7F4 transition, resulting from the distorted square antiprism [Ln/EuO8]. Both the luminous efficacy and thermal stability can be greatly enhanced via the simple composition variation. [Ln/EuO8] square antiprism‐triggered 5D0→7F2,4 transitions are elucidated in depth, acquiring ultra‐high luminous efficacy (IQE = 95%, EQE = 40%, and AE = 42%) and near‐zero thermal quenching (99%@150°C and 98%@200°C). Subsequently, the versatile utilizations in indoor lighting, plant growth lighting, and security ink are illustrated. This finding establishes a deep understanding for constructing high‐quality far‐red phosphors via the Eu3+‐centered structural units of square antiprism.