We have performed neutron diffraction isotopic substitution experiments on aerodynamically levitated droplets of CaSiO3, to directly, extract intermediate and local structural information on the Ca environment The results show a substantial broadening of the first Ca-O peak in the pair distribution function of the melt compared to the glass, which comprises primarily of 6 and 7-fold coordinated Ca-polyhedra. The broadening can be explained by a redistribution of Ca-O bond lengths, :especially toward longer distances in the liquid. The first order neutron difference function provides a test of recent molecular dynamics simulations and supports the MD model which contains short chains or channels of edge shared Ca octahedra in the liquid state. It is suggested that the polymerization of Ca polyhedra is responsible for the fragile viscosity behavior of the melt and the glass forming ability in CaSiO3.