Various high-voltage electronics for aerospace, defense, and energy storage have experienced significant miniaturization, as well as increased power draw and architectural complexity. These changes have spurred the development of thinner insulation systems with higher dielectric breakdown strengths in order to successfully protect these devices from failure. Traditional extruded insulation systems (i.e., polyethylene, polyimides, biaxially oriented polypropylene) can provide exceptional breakdown strengths, but extrusion onto smaller more complex devices results in difficulty achieving sub-micron thicknesses, low conformability to device geometry, and other fabrication challenges. We are developing an alternative to extrusion-based insulation systems that can be deposited conformally onto complex devices at varying thicknesses using polyelectrolyte-based coatings. These thinner insulation coatings can provide breakdown strengths greater than that of traditional extruded insulation systems (200-400 kV/mm) and are relatively environmentally benign.