Three‐dimensionally aligned epitaxial (Pb,La)(Zr,Ti)O3/(La,Sr)2CuO4 multilayers were grown on SrTiO3 (100) single crystals by pulse laser deposition. A cube‐on‐cube epitaxial relationship of these multilayers was confirmed by the θ‐2θ diffraction profile and the pole figure. The stability of their interfaces was confirmed by depth profiles and x‐ray diffractometry of the as‐deposited and the annealed multilayers having 100–300‐Å‐thick (La,Sr)2CuO4 layers. The results suggest that the multilayers can be applied to the ferroelectric field‐effect transistor.