Ordered nanoporous silica (MSU-H) with high surface area has been utilized as a solid substrate of a surface-modified hybrid sorbent for the application to the removal of U(VI). Carboxymethylated polyethyleneimine (CMPEI) with a strong complexing property has been introduced to the pore surface of MSU-H substrate. CMPEI-modified MSU-H (CMPEI/MSU-H) has been characterized by scanning electron microscopy and nitrogen sorption. In a kinetic experiment for 12.5 ppm U(VI) solution at pH 4.0, 99% U(VI) was removed from solution by the hybrid sorbent within less than 10 min, indicating that the sorption of U(VI) on the CMPEI/MSU-H proceeds very rapidly. It was evident that a U(VI) sorption capacity increased with pH in the range of 2.0 to 4.0. The CMPEI/MSU-H showed a high sorption capacity of 153 mg/g-sorbent at pH 4.0. In particular, the CMPEI/MSU-H showed a significantly high uranium loading stability. Only about 1% U(VI) was released out of CMPEI/MSU-H during 4 months, when the CMPEI/MSU-H was treated with polyacrylic acid.