The structure of spherical electric double layers is Studied using Monte Carlo simulation and density functional theory by considering solvent as the third component. In this molecular solvent model (MSM), ions and solvent molecules are considered as charged and neutral hard spheres, respectively, having equal diameter. The macroion is considered as an isolated hard sphere having uniform Surface charge density Surrounded by the electrolyte and the solvent. The theory is partially perturbative as the hard-sphere contribution to the one particle correlation function is evaluated using Suitably averaged weighted density, and the ionic pail is obtained through a second-order functional Taylor expansion around the bulk electrolyte. The Monte Carlo simulations have been performed in a canonical ensemble. The system is studied at varying concentrations of electrolytes, and the solvent molecules, at different valences of the electrolyte, at different macroion radii, and at varying surface charge densities. The theory is Found to be in good agreement with the simulation results over a wide range of parametric conditions. The excluded Volume effects due to the Molecular nature of the solvent are shown to have much richer features in diffuse layer phenomena like layering and charge inversion.