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Lead-free perovskites have been widely studied due to their environmental friendliness and high stability. In this study, Bi3+-doped Cs2HfCl6 has been synthesized at room temperature. Different from the emission of the Cs2HfCl6 host (452 nm), Bi3+Cs2HfCl6 can produce a bright blue emission at an excitation wavelength of 350 nm, which is derived from the 3P1 → 1S0 transition of Bi ions and accompanied by the properties of self-trapped excitons. Moreover, 7%Bi3+Cs2HfCl6 shows excellent stability with the photoluminescence quantum