In the present work, we aim to achieve the preferred crystal orientation of chemical solution deposition (CSD)-derived BaTiO3 films on ubiquitous Si wafers with the assistance of Ca2Nb3O10 nanosheet (ns-CN) template layers. The ns-CN on platinized Si (Pt/Si) substrates aligned the BaTiO3(100) plane to the substrate surface, because of the favorable lattice matching of the ns-CN (001) plane. The CSD process in air required a high crystallization temperature of 900 °C for the preferred crystal orientation of BaTiO33(100) because of the BaCO3 byproduct generated during the combustion reaction of the precursor gel. The processing in vacuum to remove CO2 species enhanced the crystal orientation even at the crystallization temperature of 800 °C, although it can generate oxygen vacancies (VO) that cause distorted polarization behavior under an applied field higher than approximately 150 kV/cm. The relative dielectric constant (ϵr) of the (100)-oriented BaTiO3 film on the ns-CN-supported Pt/Si substrate (ns-CN/Pt/Si) was generally larger than that of the randomly oriented film on Pt/Si, depending on the degree of crystal orientation.