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An effective method of improving the luminescent properties of rare earth ions in fluoride glasses were reported. The Pr3+/Ho3+ co-doped fluorochlorozirconate luminescent glasses were prepared, and the effects of chloride on the spectral properties and structure of the glasses were studied. According to the results, the glass stability is improved, and the luminescence intensity in the visible range is significantly enhanced with the introduction of chloride. By introducing 7.5 mol％ BaCl2, the luminescence intensity reaches the maximum and increases by three times. The mechanism of luminescence enhancement is explained by analyzing the correlation between the composition and the structure. The chloride ions disperse outside the glass network before the introduction of 7.5 mol％BaCl2 and increased dispersity of Pr3+and Ho3+ions in the fluorozirconate glasses.