Near-infrared (NIR) luminescent materials have attracted wide research interest due to their unique photophysical properties for designing NIR light-emitting diodes (NIR LEDs). Here, a series of Cr3+-activated NIR-emitting solid solution phosphors, Gd1-xLux(Al1-xScx)3(BO3)4:0.01Cr3+ (GLASB:Cr3+) (x = 0 to 0.5), are successfully synthesized via a cosubstitution approach. The GLASB:Cr3+ phosphors reveal extraordinary optical performance with a desirable high IQE of 93.6%, considerable broadened FWHM (from 128 nm to 196 nm) and redshift of 119 nm (747 → 866 nm) as the amount of [Lu3+-Sc3+] ion doping increases. Moreover, their photoluminescent thermal stability is substantially improved, maintaining 105.7% of the initial integral intensity up to 150 °C, namely zero-thermal-quenching. The NIR pc-LED fabricated using the GLASB:Cr3+ phosphor generates an NIR output power of 46 mW and an electro-optical efficiency of 37% at a 120 mA input current. Finally, the characteristic NIR emission of this phosphor can not only be utilized in the fields of night-vision technology and biometric identification, but also exhibits a perfect match with the absorption of the bacteriochlorophyll (BChl) and light-harvesting protein (LHP) of photosynthetic bacteria (PSB), presenting a high application prospect for improving PSB photosynthesis.