The structures of Na+[H2O](m)[C6F6](n) cluster ions were investigated using IR photodissociation (IRPD) spectroscopy in the O-H stretching region. The IRPD spectra of Na+[H2O](1)[C6F6](n) cluster ions indicate that even the addition of eight C6F6 moieties does not significantly alter the vibrational frequencies of the O-H stretches. In the case of Na+[H2O](4)[C6F6](n) clusters, no changes were observed in the symmetric stretching vibration upon addition of 1-4 C6F6's. However, the width of the asymmetric stretching vibration increased with the number of C6F6, which can be attributed to vibrational relaxation. The absence of any evidence of a significant hydrogen-bonded interaction between H2O and C6F6 for a wide range of cluster sizes and composition can best be explained as a separation between these two molecular species, that is, phase separation.