The preparation of 80nm, 140nm, and 200nm La2Zr2O7 (LZO) multilayers on biaxially textured Ni-5at%W (Ni5W) substrates using chemical solution deposition (CSD) was studied. The performance of multilayers was studied by means of X-Ray Diffraction (XRD), Electron Back Scattering Diffraction (EBSD), and Auger Electron Spectrometry (AES). The as-grown buffer layers exhibit sharp texture with texture components (0°−10°) about 96.7%, 98.9%, and 98.8%, respectively. The full-width at half maximum (FWHM) values of the ω-scans decreases with the number of layers, close to that of Ni5W substrates. The films exhibit dense, smooth, crack-free surface with a roughness Ra 3–5nm, and sufficient barrier function against metal ionic diffusion from Ni5W substrates into buffer layers. The performance of LZO multilayers was confirmed by YBa2Cu3O7−x (YBCO) films deposited by CSD technology.