Electrostatic interactions play an essential role in many analytical applications including molecular sensing and transport studies using nanopores and separation of charged species. Here, we report the voltammetric quantification of electrostatic ion enrichment in a 5-20 nm thin electrochemical cell. A simple lithographic micro/nanofabrication process was used to create ultrathin-layer cells (UTLCs) with a critical dimension (i.e., cell thickness) as small as 5 nm. The voltammetric response of a UTLC was found to be largely dominated by the electrostatic interaction between charges on the cell walls and the redox species. We show that the ultrasmall cell dimension yielded a 100-300-fold enrichment for cationic redox species. An interesting surface adsorption effect was also demonstrated.