In engineering a high-performance semiconductor device, understanding of the Fermi level position is critical. Here, we demonstrate that open-circuit potential (OCP) measurements can be used to quantify the Fermi level in nanocrystal thin films in situ during their solution-based fabrication. We use this method to study the influence of (1) a metal contact and (2) nanocrystal surface termination on the Fermi level of the nanocrystal film, and find that oxidization or reduction of the nanocrystals as well as surface terminations with dipoles can be used to tune the Fermi level over large energy ranges. Finally, to emphasize the compatibility of the technique with device fabrication, we show that we can use blends of ligands to design the Fermi level landscape in a nanocrystal film. Our work highlights that OCP measurements can be used to gain insight into existing device operation and direct further optimization of optoelectronic devices.