A novel route to organic-inorganic composites was described based on biomineralization of poly(ethylene glycol) (PEG)-based hydrogels. The 3-dimensional hydrogels were synthesized by radical crosslinking polymerization of poly(ethylene glycol fumarate) (PEGF) in the presence of ethylene glycol methacrylate phosphate (EGMP) as an apatite-nuclating monomer, acrylamide (AAm) as a composition-modulating comonomer, and potassium persulfate (PPS) as a radical initiator. We used the urea-mediated solution precipitation technique for biomineralization of hydrogels. The apatite grown on the surface and interior of the hydrogel was similar to biological apatites in the composition and crystalline structure. Powder x-ray diffraction (XRD) showed that the calcium phosphate crystalline platelets on hydrogels are preferentially aligned along the crystallographic c-axis direction. Inductively-coupled plasma mass spectroscopy (ICP-MS) analysis showed that the Ca/P molar ratio of apatites grown on the hydrogel template was found to be 1.60, which is identical to that of natural bones. In vitro cell experiments showed that the cell adhesion/proliferation on the mineralized hydrogel was more pronounced than on the pure polymer hydrogel.