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ABSTRACT: Study on the correlation between ionic conduction and nonlinear optical (NLO) constants has been extended to fluoride materials. It is found that the activation energy of ion transport decreases with the increase of the NLO constants. To understand the origin of the relationship, the NLO constants of fluoride ion conductors are investigated by using the sheik-Bahae equation, which has been used successfully in the study of nonlinear refractive indexes of semiconductors. The analysis reveals that the bond fluctuation model of superionic conductors provides a basis to understand the observed behavior.