The interaction of OH - with Fe(TPP) + , Fe(TDCPP) + , Fe(TMP) + and Fe(TFPP) + in 1,2-dichloroethane was studied by titrating FeP solutions with aliquots of a solution of tetrabutylammonium hydroxide in acetonitrile. The number of OH - ions (n) coordinated to the FeP and the stability constants (β n ) for the FeP-OH - complexes were calculated from UV-Vis absorbance data and iron spin states were determined through EPR spectroscopy. Fe(TMP) + forms a high-spin mono-hydroxo complex, while Fe(TPP) + and Fe(TDCPP) + form high-spin bis-hydroxo complexes. To our knowledge, this is the first time that the formation of bis-hydroxo complexes from Fe(TPP) + has been reported, and this was possible because the studies were carried out in basic organic media. In this same medium, Fe I I I -Fe I I reduction upon OH - addition to Fe(TFPP) + was observed, without concomitant formation of the μ-oxo dimeric species [Fe(TFPP)] 2 O.