Freestanding BaTiO3 ceramics films were fabricated using the aerosol deposition (AD) method and the size effect of nanograined BaTiO3 ceramics was demonstrated. Dense BaTiO3 thick film fabricated by the AD method was crystallized and detached from substrate by an annealing treatment at 600 °C, and then the grain size was controlled by a reannealing treatment at various temperatures. As a result, freestanding BaTiO3 thick films with various grain sizes from 24 to 170 nm were successfully obtained. Polarization–electric field (P–E) measurement revealed that BaTiO3 ceramics with grain sizes of more than 58 nm showed ferroelectricity, whereas BaTiO3 ceramics with an average grain size of 24 nm showed paraelectricity at room temperature. Dielectric measurement indicated that the permittivity decreased with decreasing grain size in the range of 170 to 24 nm.