The use of bismuth in medicinal applications has been limited despite the many promising indications of its effectiveness in treatments for a large number of ailments. This is predominantly due to the lack of understanding of bismuth chemistry, including thermodynamic and kinetic aspects, thus hindering the design of improved drugs. This, in turn, is due to the difficulty in studying the complex chemistry of this element. Bismuth undergoes hydrolysis from below pH 1 and forms precipitates around pH 2 already, thus has to be studied from low pH. The most commonly used technique to determine stability constants, namely glass electrode potentiometry, cannot be employed in very acidic solutions. Complex formation has previously been studied by polarography where potential shifts and changes in current are used to determine solution species and evaluate stability constants. The benefits of employing polarography here are that low bismuth concentrations can be used to postpone precipitation and it can be used across the pH range. However, the diffusion junction potential becomes significant below pH 2 and changes with pH. Protocols to determine the stability of bismuth complexes using polarography were developed in this study. Firstly, the junction potential cannot be measured directly, so a witness metal ion was introduced into the solution to monitor its magnitude with changing pH. For this thallium (I) was used as it does not readily undergo complexation and hence potential shifts observed with changing pH is due to changes in the junction potential. This process was successfully tested on the cadmium(II)-picolinic acid system. Secondly, it was suggested that the reduction of bismuth(III) is quasi-reversible, so mechanisms of determining the reversible reduction potentials were investigated using the copper(II)-picolinic acid system, as copper(II) has a reduction potential almost identical to bismuth(III) and its reduction is also quasi-reversible. However, it was found that bismuth was reversibly reduced under the polarographic conditions employed. Thirdly, the free bismuth(III) potential had to be determined in order to calculate potential shifts due to complex formation. This potential cannot be measured directly either, so procedures were developed to determine this value by accounting for both hydrolysis and complex formation with the background electrolyte anion (nitrate). Three bismuth-ligand systems were studied where the ligands were picolinic acid, dipicolinic acid and quinolinic acid. It was necessary to determine the stability constants for these systems by using a combination of direct polarographic data interpretation and the use of virtual potentiometry.