Abstract Manganese‐based halides present promising applications in flexible devices in versatile scenarios due to their low toxicity, high quantum yield, facile synthesis, and compatibility with multiple excitation sources. Herein, two novel manganese‐based halides are synthesized, namely (CTP) 2 MnCl 4 and (BTP) 2 MnCl 4 (CTP = (2‐chlorobenzyl)triphenylphosphonium, BTP = benzyltriphenylphosphonium), utilizing a solvent evaporation method. High photoluminescence quantum yields are achieved, ≈98.5% and 88.4%, respectively. Upon mechanical stimulations, both materials exhibited intense green emission attributed to the recombination of electrons and holes. Effective force‐induced luminescence can be realized using a flexible, force‐responsive film derived from the two compounds. In addition, the (CTP) 2 MnCl 4 and (BTP) 2 MnCl 4 crystals exhibited remarkable X‐ray scintillation properties. Based on commercial CsI, Tl scintillator standards, the calculated light yields for (CTP) 2 MnCl 4 and (BTP) 2 MnCl 4 single crystals are ≈89 000 and 49 000 photons/MeV, respectively. A flexible scintillation film is fabricated with (CTP) 2 MnCl 4 and polydimethylsiloxane. Furthermore, a light‐emitting fiber film with a large area of 20 cm × 25 cm is fabricated using (CTP) 2 MnCl 4 and polymethyl methacrylate via an electrospinning method. The film is suitable for applications in emergency rescue, information recording, and emergency lighting. This research provides a new approach for synthesizing large‐sized, high‐performance luminescence materials with multiple excitation sources and their versatile applications.