Abstract Screen printing is considered a cost-effective and environmentally friendly method for fabricating oriented thick-film patterns. However, the universal factors governing thick-film formation have not been clarified yet. This study investigates preferential orientation by fabricating various Pb-based piezoelectric thick films, such as PZT and PMN–PT, on (100) pc -oriented BaTiO 3 (BT) templates. To clarify orientation behavior, a novel first-principles computational approach evaluated surface free energies while preventing artificial structural collapse on slab surfaces. High-temperature X-ray diffraction revealed that lattice matching alone does not determine orientation behavior. Instead, first-principles calculations showed that orientation is governed by the balance of surface free energies (wettability) between the BT template and the overlying thick film. Materials exhibiting the layer-by-layer growth mode form highly oriented thick films, whereas the island-like growth mode accounts for randomly oriented films. These findings provide guidelines for material selection not only in oriented thick-film fabrication but also in solid-state single crystal growth methods.