<p>Organic room-temperature phosphorescent materials have developed rapidly. However, the phosphor emission enhancement of micro-nano materials achieved by electrostatic interaction were rarely reported. Herein, taking polystyrene microspheres (μPS) and urea-formaldehyde phosphorescent resin microspheres (μUF) as examples, a method was developed to enhance the phosphorescent performance of μUF by mixing with μPS. The opposite surface potential of μPS and μUF resulting in a significant electrostatic interaction. Moreover, the guest molecules in μUF were polarized under electrostatic interaction, which enhanced the binding to the matrix and further suppressed the non-radiative transition, so effectively improving phosphor emission. Furthermore, the electrostatic interaction of micro-nano composites demonstrated good universality in improving phosphorescence performance, as evidenced by incorporating of varying polymer microparticles into μUF or blending μPS with other phosphorescent microspheres. This work demonstrates the mechanism of electrostatic interaction enhancing phosphorescence emission within the micro-nano composites, which paves the way for the regulation of phosphorescent materials.</p>