Realizing ratiometric thermometers using single-component organic solid-state luminophores is attractive but challenging. Here, we synthesized a series of N,C-chelated tetra-coordinated organoboron compounds and characterized their structures. Among them, sample BN2Br can be used as a luminescent thermometer and exhibits a high temperature sensitivity (3.67% K-1), a wide response range of 120-280 K, and good reversibility, which is mainly due to the temperature-dependent intermolecular stacking effect in the solid state. The proposed ratiometric thermometry protocol may provide new insights for developing photonic thermometers.