Protein monolayer electrochemistry (PME) is a strategy of studying the electrochemistry of biomolecules by using self-assembled monolayers (SAMs) as an adsorption platform. In this work, we seek to create a more efficient PME system by modifying electrodes with films constructed from specifically designed nanoparticles called monolayer protected clusters (MPCs). A key component of well-defined protein electrochemistry is the effective discrimination of the non-faradaic background current. Controlling this charging current in MPC films is the focus of our investigation with a key finding being that this background signal is directly related to the architecture of the assembled MPC film. MPC film systems were optimized for subsequent protein electrochemistry by examining the charging current of films assembled with three different linking mechanisms as well as exploring the effects of individual MPC features such as ligand chain length and core size. Films optimized to exhibit low charging current were subsequently engineered for the adsorption and electrochemical analysis of a simple redox protein, cytochrome c (Cc). The direct electrochemistry of surface confined redox proteins is an important concept for many bioanalytical based studies, including biosensor technology development and fundamental electron transfer models.