An exceptional high ferroelectric remnant polarization (P-r) was observed in BaTiO3 ceramics owing to the formation of micron-sized grains possessing nano-scale mosaicity. Such a structural hierarchy was developed via a novel crystal-growth mechanism, namely ordered coalescence of nano-crystals achieved by synergetic atomic epitaxial growth and self-assembly of nano-crystals. The accommodating lattice defects in sub-grain boundaries due to the imperfect assembly of nano-crystals significantly contribute to the P-r enhancement by stimulating the dynamics of ferroelectric domain formation and switching. This finding defines a new approach to nanopowder sintering leading to enhanced properties sensitive to lattice defects.