We present a theoretical investigation of the orbital ordering occurring in Sr(3)Cr(2)O(8) based on density functional theory calculations. We demonstrate that the strong electron correlation arising within the Cr-3d shell can clearly explain both the phase transition leading to the stabilization of its monoclinic C2/c space-group symmetry and its spin-singlet magnetic ground state. The relevance of the electronic structure determined theoretically is further established by comparison to high-resolution electron energy loss spectroscopy measurements.