Lead-free Halides, especially Mn-based ones, are preferred as hotspots in the exploration of photoluminescent materials. However, there are few reports on sensitive reversible thermochromism and switchable dual emission originating from self-trapped exciton emission in pure Mn-Based materials. Here, we report a new Mn-based hybrid material [TMPA]2MnI4 (TMPA = trimethylphenylammonium), which shows two emission peaks at 545 and 660 nm benefitting from the d-d orbital transition of Mn2+ and the generation of self-trapped excitons, respectively. Due to the different sensitivity to temperature, the stages of thermal activation and thermal quenching of the two emission types are also inconsistent, showing a certain competition relationship and dominating the emission colors in different temperature ranges, resulting in adjustable green-orange-green thermochromic luminescence from 100 to 403 K (both high and low temperatures correspond to green, and orange is displayed at near room temperature). Therefore, thermochromic luminescence can be easily achieved by controlling the temperature under the guidance of excited states. This work provides new insights into the synthesis and application of thermochromic materials. Therefore, it is certain that regulating temperature while being guided by excited states will achieve thermochromic luminescence. This research offers fresh perspectives on the development and potential of thermochromic materials.