A novel proton exchange membrane(PEM)was designed and prepared from a polymer containing calix[4]arene as the functional unit to transport proton.The proton-conductivity of this membrane is about the same order of magnitude as that of Nafion(R)112 membrane.It is of interest to note that very different from most of the currently known PEMs,this membrane can transport proton without the help of water or other solvents.It is deduced that the protons are transported via an ion tunneling model.This opens up a new avenue for a new type of solvent-free PEMs to be applied in the development of new H2/O2 fuel cells.