The second near-infrared (NIR II) response photon up-conversion (UC) materials show great application prospects in the fields of biology and optical communication. However, it is still an enormous challenge to obtain efficient NIR II response materials. Herein, we develop a series of Er³⁺ doped ternary sulfides phosphors with highly efficient UC emissions under 1532 nm irradiation. β-NaYS₂:Er³⁺ achieves a visible UC efficiency as high as 2.6%, along with high brightness, spectral stability of lights illumination and temperature. Such efficient UC is dominated by excited state absorption, accompanied by the advantage of long lifetimes (⁴I_9/2, 9.24 ms; ⁴I_13/2, 30.27 ms) of excited state levels of Er³⁺, instead of the well-recognized energy transfer UC between sensitizer and activator. NaYS₂:Er³⁺ phosphors are further developed for high-performance underwater communication and narrowband NIR photodetectors. Our findings suggest a novel approach for developing NIR II response UC materials, and simulate new applications, eg., simultaneous NIR and visible optical communication.