2,2'-(Pyridyl)benzimidazole is used as a probe to explore proton transfer through nafion membranes. The probe marks the availability of water in native as well as cation-exchanged membrane. Using steady state and time-resolved fluorescence studies, it has been shown that the rotation of the pyridyl and benzimidazole rings with respect to each other, which is ultrafast in higher water contents, is hindered as the water content in the membranes is decreased. In cation-exchanged membranes, it is observed that the formation of the ESPT (excited state proton transfer) state is reduced to a large extent. Thus, it may be inferred that the proton transport is observed to be hindered even in molecular dimensions of one water molecule thereby bolstering the contention that it may not be essential for water channels to break for proton conductivity to decrease.