The device of reliable non-contact ratiometric optical thermometry technique gradually became a cutting-edge research pot over decades due to its intriguing features of rapid response, high accuracy and simple operation. In which, Boltzmann-based optical thermometry has attracted widespread attention for its exceptional reliability. Here in, we put forward an effective ratiometric optical thermometry based on the highly sensitive and effective Boltzmann-based 2E→4A2/4T2→4A2 emission ratio of BaAl3.9Sb2O12:0.1Cr3+. The phosphor shows dual near-infrared luminescence lines at 698 nm and 710 nm (2E→4A2) and the luminescence band near 750 nm (4T2→4A2). With the temperature elevating from 170 to 470 K, the emission intensity of luminescence lines undergoes continuous enhancement and possess excellent anti-thermal quenching property (3.5-fold at 470 K, compared to 170 K). In contrast, the emission intensity of luminescence band shows a monotonic decline trend. The luminescence intensity ratio shows a good linear relationship in the Arrhenius diagram, and the relative sensitivity reaches 2.08 % K−1 at 170 K, which corroborates the BaAl3.9Sb2O12:0.1Cr3+ has the potential as the optical cryogenic thermometer. In the end, the work provides some insights into the development of novel Cr3+-doped thermometry materials based on the 2E and 4T2 energy level transitions in intermediate crystal field environments.