The preparation of tetragonal barium titanate (BT) powders with uniform and suitable particle sizes is a significant prerequisite for ultra-thin and highly integrated multilayer ceramic capacitors (MLCCs). However, the balance of high tetragonality and controllable particle size remains a challenge, which limits the practical application of BT powders. Herein, the effects of different proportions of hydrothermal medium composition on the hydroxylation process are explored to obtain high tetragonality. The high tetragonality of BT powders under the optimal solvent condition of water:ethanol:ammonia solution of 2:2:1 is around 1.009 and increases with the particle size. Meanwhile, the good uniformity and dispersion of BT powders with particle sizes of 160, 190, 220, and 250 nm benefit from the inhibition of ethanol on the interfacial activity of BT particles (BTPs). The core–shell structure of BTPs is revealed by different lattice fringe spacings of the core and edge and the crystal structure by reconstructed atomic arrangement, which reasonably explains the trend between tetragonality and average particle size. These findings are instructive for the related research on the hydrothermal process of BT powders.