The miniaturization and demand for high-performance BaTiO 3 (BTO)-based multilayer chips have evoked tremendous research to further scale down the size of the BTO nano-particles (NPs) by wet chemical techniques. However, synthesizing narrowly dispersed tetragonal-BTO NPs with nano-scale size is still challenging. In this work, a maleic acid-assisted modified coprecipitation (CP) route armed with freeze-drying was carried out to obtain BTO NPs with a mean size of ∼170 nm and a high c/a ratio of 1.0109. In addition, the synergetic effect of freeze-drying accompanied by glucose as an aggregation inhibitor resulted in ultra-fine (∼44 nm) narrowly dispersed tetragonal BTO, which to the best of our knowledge is the finest compared with those obtained by CP methods and even hydrothermal method. The maximum permittivity of >12,000 with low dielectric loss (0.03) can be obtained for the asobtained BTO-Fr-Gl-pH9-1400C ceramic pellet. This modified synthetic strategy and the obtained powder are promising for further scaling the BTO-based multilayer chips.