Electrochemical and spectroelectrochemical properties of three open-chain pentapyrroles and the corresponding sapphyrins were examined in pyridine containing 0.1 M tetra-n-butylammonium perchlorate and dichloromethane (CH2Cl2) or benzonitrile (PhCN) containing tetra-n-butylammonium hydroxide (TBAOH). The investigated compounds are represented as (Ar)(4)PPyH3 and (Ar)(4)SH3, where Ar is a F- or Cl- substituted phenyl group, PPy is a trianion of the open-chain pentapyrrole, and S is a trianion of the sapphyrin. The pentapyrroles, (Ar)(4)PPyH3, undergo two reversible one-electron reductions in pyridine, while the structurally related sapphyrins exhibit four reductions in this solvent, the first two of which are irreversible due to coupled chemical reactions following the electron transfers. Both series of neutral compounds could be deprotonated in CH2Cl2 or PhCN by addition of TBAOH to solution, and the progress of these reactions was monitored as a function of the base concentration by cyclic voltammetry and UV-vis spectroscopy. The neutral pentapyrroles were spectroscopically shown to undergo a loss of two protons in a single step to generate the [(Ar)(4)PPyH](2-) dianion while the sapphyrins could only be monodeprotonated, leading to formation of the [(Ar)(4)SH2](-) monoanion under the same solution conditions. The deprotonation constants were measured for each series of compounds in benzonitrile, and oxidation-reduction mechanisms are examined as a function of the solution 'basicity'.