X-ray diffraction measurements performed on aerodynamically levitated CaSiO(3) droplets have been interpreted using a structurally heterogeneous liquid-state model. When cooled, the high-temperature liquid shows evidence of the polymerization of edge shared Ca octahedra. Diffraction isosbestic points are used to characterize the polymerization process in the pair-distribution function. This behavior is linear in the high-temperature melt but exhibits rapid growth just above the glass transition temperature around 1.2T(g). The heterogeneous liquid interpretation is supported by molecular-dynamics simulations which show the CaSiO(3) glass has more edge-shared polyhedra and fewer corner shared polyhedra than the liquid model.