In the process of recovering uranium resources from uranium-containing wastewater (UCW) via adsorption methods, it is imperative to address challenges related to the stability and selectivity of adsorbents in the separation of uranium ions. Xerogel porous adsorbents have garnered significant research interest for their potential application in uranium ion adsorption, owing to their high porosity, robust plasticity, and abundant functional groups. Based on the efficient separation of uranium by acid-resistant polyvinyl alcohol/chitosan (PVA/CS) xerogel, polyethyleneimine (PEI) was selected to adjust its pores. By examining the characteristics of the modified xerogel both prior to and following U(VI) adsorption, optimizing the conditions for its U(VI) adsorption, and analyzing the separation mechanism of U(VI), the results demonstrate that PEI can effectively modify the pore environment of PVA/CS xerogel. Furthermore, PEI-PVA/CS xerogel maintains consistent U(VI) separation efficacy in UCW across a pH range of 2–7. After five cycles of uranium desorption and adsorption, the adsorption recovery capacity exceeds 97.7 %, with minimal interference from cations. The synergistic effect of -NH2 and -OH functional groups is responsible for the efficient separation of U(VI) by PEI-PVA/CS xerogel. This xerogel demonstrates the stability and selectivity required for U(VI) adsorbents, indicating its potential for engineering applications in UCW treatment.