A series of poly(acrylic acid-co-acrylamide)/ kaolin [poly(AA-co-Am)/kaolin] composites were prepared by aqueous solution copolymerization of partially neutralized acrylic acid and acrylamide in the presence of kaolin nanopowder, which was synthesized to act as a release carrier of urea fertilizer. The superabsorbent composite was swollen in aqueous solution of urea to load urea, and the effect of urea concentration on the swelling was investigated. Furthermore, the effects of the contents of crosslinker, kaolin, and acrylamide, the neutralization degree of acrylic acid, and temperature, pH, and ionic strength of release medium on water absorbency and diffusion coefficient of urea release from poly(AA-co-Am)/kaolin were studied systematically. It was found that urea loading percentage could be adjusted by urea concentration of swelling medium, and urea diffusion coefficient could be regulated through the contents of crosslinker, kaolin, and acrylamide, and the neutralization degree of acrylic acid. Additionally, temperature and ionic strength of release medium may also affect the urea release process. The conclusions obtained could provide theoretical basis for urea diffusion behavior in superabsorbent used in agriculture.