Emission from ion-pair states of I-2 is observed when HI clusters are photolyzed at 248 nm. The emission depends quadratically on the laser intensity and quartically on the stagnation pressure of neat HI. The results strongly suggest that the four-center photoinduced reaction (HI)(2) --> H-2 + I-2* takes place in HI clusters, followed by excitation of the I-2* to the ion-pair levels.