The effect of A-site substitution of Ce3+ in tungsten bronze structured PBN ceramics with the general formula, Pb(x - 3y/2) CeyBa(1 - x) Nb2O6 and the stoichiometric chemical formula, Pb(0.65 - 3y/2) CeyBa0.35Nb2O6, where y = 0, 2, 4, 6, 8 and 10 mol% ceramic compositions synthesized through solid state reaction method are reported. The X-ray diffraction studies exhibited the presence of an orthorhombic phase, and its intensity increased with the increasing Ce3+ content up to y = 6 mol% or A(3) composition. The lattice parameters, unit cell volume and density as a function of Ce3+ concentration are discussed. It is observed that increasing Ce3+ content in A-site influenced the dielectric properties. The optimum dielectric properties of room temperature dielectric constant (epsilon(RT)) and dielectric maximum (epsilon T-c) are observed in y = 6 mol% or A(3) composition while Curie temperature (T-c) and dielectric loss (tan delta) constantly decreased from undoped to y = 10 mol%, and thus A(3) composition or 6 mol% Ce modified tungsten bronze structured-PBN could be suitable for capacitor applications.