Erbium ions are commonly used to extend the photoelectric properties of metal halide perovskites from visible to near-infrared (NIR) range. However, achieving high-efficiency multi-mode luminescence in a single system is difficult due to the weak absorption associated with forbidden 4f-4f transitions. In this study, a unique strategy is proposed to adjust multi-mode luminescence and enhance NIR-II emission in Cs2NaBiCl6 by incorporating Fe3+ ions. The as-prepared material demonstrates reversible thermochromism, driven by strong electron-phonon coupling effect, and exhibits tunable luminescence that can be adjusted by altering excitation energy and temperature. Notably, benefitting from the charge transfer transition of Fe3+-Cl- along with the influence of Fe3+ doping on the geometrical and electronic structures, the blue-excitable (450 nm) NIR-II emission around 1541 nm from Er3+ is realized for the first time, achieving an intensity 16.7 times higher and a maximum photoluminescence quantum yield of 22.5%. This enhancement enables innovative applications such as two-dimensional information encryption by the multi-channel cooperative responses and improved NIR imaging. The study highlights the potential of Fe3+ doping in optimizing absorption and multi-mode luminescence in perovskites, opening avenues for advanced applications in blue-excitable NIR light emitting diodes, thermometer, anti-counterfeiting, and NIR imaging.