The electrochemical quartz crystal microbalance (QCM) was used to investigate the deposition of poly(allylamine hydrochloride) (PAH) with molybdate anions under anodic conditions. The PAH-molybdate complex was used as a model system to understand possible deposition criteria which may be relevant to the formation of proteinaceous films on CoCrMo hip implants. Data indicate that PAH deposition will occur above ∼0.60 V vs SCE if molybdate anions are present in the electrolyte above a critical concentration, and if the polymer concentration remains below a critical value. Numerical modeling and dynamic light scattering (DLS) studies were performed to understand the conditions that enable deposition to occur at these potentials. The results indicate that PAH-molybdate complexes form most efficiently when the polyvalent positive charge and polyvalent negative charge in the system are in an optimum range with respect to each other.