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Long chain organic poly(ammonium phosphate)s (1a–g and 2) were prepared by a precipitation technique by reaction of poly(lithium phosphate) with organic ammonium salts. Their compositions were established by nitrogen and phosphorus analyses and their polymeric nature was confirmed by molecular weight determinations via end group titrations and by the viscosity method. Studies of conductance at different concentrations indicated their polyelectrolytic behaviour. Paper chromatographic studies supplied additional evidence of a long chain polymeric structure, like Graham's salt and poly(lithium phosphate).