The electrochemistry and UV - vis spectral properties of neutral and electroreduced Al( III) phthalocyanine, ( Pc) AlCl, were characterized in four different nonaqueous solvents ( THF, DMSO, DMF, and pyridine) containing tetra-n-butylammonium perchlorate, as well as in THF containing 0.4 M TBAP and the more strongly coordinating Cl-, F-, OH-, or CN- anions added to solution in the form of a tetra-n-butylammonium salt. The initial phthalocyanine added to solution is represented as ( Pc) AlCl, but the actual electroactive form of the compound varied as a function of both the solvent and type or number of bound anionic axial ligands. An uncharged ( Pc) AlCl( THF) or ( Pc) Al( CN)( THF) complex is present in THF solutions containing 0.4 M TBAP and excess Cl- or CN-, while transient mu-oxo dimers are spectroscopically observed upon addition of OH- or F- to ( Pc) AlCl( THF) in THF followed by the ultimate formation of stable six-coordinate anionic species represented as [( Pc) Al( OH)(2)](-) or [( Pc) AIF(2)](-). Each phthalocyanine undergoes three reversible one-electron additions at the conjugated Pc macrocycle within the negative potential limit of the solvent, and the UV - vis spectral changes obtained during the first two reductions were recorded in a thin-layer cell to evaluate the prevailing electron-transfer mechanisms.