Salt-free polyelectrolyte behaviour which is typically observed at low polymer concentrations for polyelectrolyte aqueous solutions and random ionomer non-aqueous solutions (in polar solvents) (i.e., negative angular dependence of the reciprocal scattering in static light scattering and an appearance of the fast mode in dynamic light scattering) has been observed for monotelechelic ionomer solutions in a polar solvent. This indicates that only single charge (per chain) is sufficient to produce intermolecular electrostatic interactions, which are responsible for such characteristic behaviour. However, the ’characteristic’ behaviour, which is typically observed at higher concentrations for polyelectrolyte and random ionomer solutions (i.e., large positive apparent radius of gyration in static scattering and appearance of the slow mode in addition to the fast mode in dynamic scattering) has not been observed to date for monotelechelic ionomer solutions. The absence of high-concentration characteristics for the monotelechelic ionomer solutions gives additional insight as to the nature and structure of ’heterogeneities’ in salt-free polyelectrolyte solutions, which is still controversial.