AbstractThe construction of multi‐decay pathways of smart organic light‐emitting materials has drawn intensive research enthusiasm owing to their substantial promise in diverse optoelectronic applications. Nowadays, numerous chemical substances have been refined to extend and enhance their intriguing luminescent properties. Nowadays, plenty of chemicals have been adapted to amplify more interesting luminescent properties. How to utilize an easy way to tune multi‐decay pathways resulting in various emissions is still challenging. Here, we present a triphenylamine derivative, TPA3BP, which exhibits a variety of multi‐decay pathways in different states and can exhibit thermally activated delayed fluorescence in both the polydimethylsiloxane and crystalline state, but also achieve room temperature phosphorescence by embedding it into the poly (methyl methacrylate) (PMMA) and polyvinyl pyrrolidone matrix. The multi‐decay luminescence can be attributed to the dual effect arising from the n‐π* transition of TPA3BP and the regulation of molecular transition pathways within the matrix environment. This intriguing phenomenon highlights the combined influence of TPA3BP's electronic transitions and the influence of the polarity and rigidity of the surrounding matrix on the observed characteristics. This advancement has widened the structural possibilities for multi‐decay luminescent materials, enabling their targeted synthesis for future applications, such as information encryption and smart anti‐counterfeiting.