Infrared hole-burning studies of the ionic polymers poly(ammonium styrenesulfonate) and ammonium Nafion are reported. The ammonium groups are doped with a few percent of deuterium, and the irradiation is in the N-D stretching bands. Both polymers show only broad spectral absorption bands, but the narrow spectral holes reveal details of the ammonium group interactions with their surroundings. The results are interpreted by comparison with the hole burning of the model compounds ammonium tosylate and ammonium triflate. Characteristic behavior of the holes shows that some of the local conformations of the models persist in the polymers. Particularly unusual are the changes of hole depth with time : for the Nafion, some holes decay for a period of time, then grow, and then continue to decay--a behavior also observed in the model triflate.