A novel type of calcium phosphate-organic polymer composite having a hierarchical structure was prepared by calcification of a poly(acrylic acid) hydrogel. Macroscopically, an organic gel containing phosphate ions was transformed into an opaque solid material by diffusion of calcium ions. We observed the formation of micrometer-scale layered structures consisting of nanoscale crystals of hydroxylapatite (HAp) in the opaque products. The laminated architecture resulting from the periodic precipitation of calcium phosphate varied with the reaction conditions, such as the concentrations of the precursor ions and the density of the gel. The nanoscopic structure of HAp crystals was modified by the addition of gelatin to the polymer matrix. q