Ion conductivity and electrical relaxation have been studied in poly(propylene glycol) 4000 (PPG) complexed with NH4CF3SO3 in a concentration range of O:M=9800 to 10. A dielectric relaxation peak at about 1 MHz at room temperature is suggested to be due to ion pairs. Results indicate that the electrical relaxation times associated with these peaks could act as a probe for the local flexibility of the polymer chains and that, in the concentration range studied, the fraction of ion pairs increases with increasing salt concentration. Other features of ion association are inferred from an analysis due to Pettit and Bruckenstein. Ion conductivity in NH4SF3SO3, complexed with PPG is enhanced by a factor of 3 to 4 over that measured for LiCF3SO3 complexed PPG. Ion conductivity in ND4CF3SO3 complexed PPG is used to comment on proton conduction in these systems.