Recently, the use of small-sized BaTiO3 particles for ultra-thin MLCC research has increased as a method for minimizing the dielectric layer’s thickness in thick film process. However, when particles smaller than 100 nm are used, the reduced particle size leads to a reduced dielectric constant. The use of nanoparticles, therefore, requires an increase in the amount of additive used due to the increase in the specific surface area, thus increasing the production cost. In this study, a novel method of coating 150-nm and 80-nm BaTiO3 powders with additives and mixing them together was employed, taking advantage of the effect obtained through the use of BaTiO3 particles smaller than 100 nm, to conveniently obtain the desired dielectric constant and thermal characteristics. Also, the microstructure and the dielectric properties were evaluated. The additives Dy, Mn, Mg, Si, and Cr were coated on a 150-nm powder, and the additives Dy, Mn, Mg, and Si were coated on 80-nm powder, followed by mixing at a ratio of 1:1. As a result, the microstructure revealed grain formation according to the liquid-phase additive Si; additionally, densification was well realized. However, non-reducibility was not obtained, and the material became a semiconductor. When the amount of added Mn in the 150-nm powder was increased to 0.2 and 0.3 mol%, insignificant changes in the microstructure were observed, and the bulk density after mixing was found to have increased drastically in comparison to that before mixing. Also, non-reducibility was obtained for certain conditions. The dielectric property was found to be consistent with the densification and the grain size. The mixed composition #1-0.3 had a dielectric constant over 2000, and the result somewhat satisfied the dielectric constant temperature dependency for X6S.