Very recently, we have found that the high density 2DEG (ne ∼1021 cm−3), which is confined within a unit cell layer thickness of SrTiO3, exhibits unusually large Seebeck coefficient (S2DEG/Sbulk ∼5). In the optimum, extremely high ZT2DEG of ∼2.4 can be obtained at room temperature, while the effective ZTeff. was only ∼0.24 because 9 unit cells of electrically insulating SrTiO3 layers were used to fabricate the 2DEG structure. Thus, high ZTeff can be realized if the insulating layer thickness is reduced significantly. We selected BaTiO3∼SrTiO3:Nb superlattice to reduce insulating layer thickness because dielectric constant of BaTiO3 is one order of magnitude large (∼3,000) as compared to that of SrTiO3 (∼300). We expected that the conduction electrons can be confined much strongly in the SrTiO3:Nb layer by sandwiching between highly dielectric BaTiO3 layers. As a result, we clarified that the critical BaTiO3 layer thickness is 1.2 nm, significantly small as compared to SrTiO3 layer (4 nm). The BaTiO3/SrTiO3:Nb superlattice films were fabricated by a pulsed laser deposition (PLD) method on (001)-face of LaAlO3 single crystal substrate at 900°C. During the film growth, we monitored RHEED intensity oscillation to control layer thickness precisely. Out-of-plane high-resolution X-ray diffraction measurements and cross sectional HAADF-STEM observations revealed that the resultant films were high quality BaTiO3/SrTiO3:Nb superlattice. Hall mobility of the SrTiO3:Nb layer was 0.4 cm2·V−1·s−1, while that of superlattice decreased gradually with increasing BaTiO3 layer thickness most likely due to that intra layer diffusion of Ba2+ ion occurred between BaTiO3 and SrTiO3:Nb layers, which was clearly observed by the EELS mapping. Seebeck coefficient |S|300K of SrTiO3:Nb layer was 57 μV·K−1, which corresponds carrier concentration ne of 5×1021 cm−3. The |S|300K value became large with decreasing the SrTiO3:Nb layer thickness (dSrTiO3:Nb) and it reached 305 μV·K−1, which is approximately 5 times larger than that of SrTiO3:Nb bulk. The slope of log |S|- log dSrTiO3:Nb plots was 1/2, suggesting that quantum size effect occurred. Critical BaTiO3 layer thickness for the quantum confinement of the electrons was 1.2 nm (3 unit cells of BaTiO3), which is significantly small as compared to SrTiO3 (4 nm). Thus, BaTiO3/SrTiO3:Nb superlattice would be a promising candidate to realize high ZTeff.