The synthesis of a novel highly swelling, macroporous hydrogel from poly(allylamine) using 3-chloropentan-2,4-dione as a crosslinker is reported. The swelling of the hydrogel was sensitive to changes in pH, temperature, and the extent of crosslinking. The dry gel exhibited a regular honeycomb network with smooth macropores. The hydrogel was inherently luminescent, and so was a metal polychelate.