In order to obtain information about aluminum(III)-phosphate interactions, potentiometric measurements were carried out to characterize the complex forming properties of Al(III) with organic phosphates, phosphonates, and nucleoside-5’-monophosphates. The aluminum(III)-orthophosphate system is difficult to study due to AlPO4 precipitation. To overcome this problem, the stability constant logarithms of the 1:1 Al(III) complexes of ligands with the same donor groups (log K-1:1) were plotted-against the basicities of the ligands (log K-PO3H) The resulting linear free energy relation (LFER) indicates that organic phosphates, phosphonates, and uridine-, thymidine-, and guanosine 5’-monophosphates similarly bind Al(III). Adenosine and cytidine 5’-monophosphate fall above the LFER owing to the presence of a second microform with the nucleic base protonated and a hydroxide bound to the Al(III). From the LFER the log stability constant for Al(III) binding to HPO42- is estimated as 6.13 +/- 0.05. From the weakness of any soluble orthophosphate complexes of Al(III) we confirm the importance of citrate as the main small molecule Al3+ binder in the blood serum. The study includes investigation of Al(III) binding to di- and triphosphates, which bind metal ion differently than monophosphates. Structures of the complexes were supported by P-31 NMR measurements.