The size effect of BaTiO3 (BTO) is the most important issue to design multilayer ceramic capacitors (MLCCs) with high capacitance. In the size effect of BTO particles, the size dependence of dielectric permittivity related with the complex structure in BTO nano-particles. The grain size dependence of dielectric permittivity in BTO ceramics was due to the domain wall contribution. The core-shell structure played an important role in the size effect of dielectric layers in X7R-MLCCs. Computer simulation technique was developed to predict the limit of capacitance density of MLCCs produced by the current technology. Dielectric properties of MLCCs with different particle size of BTO were measured, and the data were analyzed using B-SPLINE fitting to predict dielectric permittivity at arbitrary temperatures and AC-fields. The dielectric properties of barium titanate grains smaller than 100 nm were predicted using least squares fitting of the B-SPLINE coefficients. It was found from the simulation that the use of barium titanate grains smaller than 80 nm did not give an advantage to increase the capacitance density as well as temperature stability of the MLCCs. The maximum capacitance was predicted for the 1608 (mm) chip size.