The most important interface-related quantities determined by band alignment are the barrier heights for charge trans- port, given by the Fermi level position at the interface. Taking Pb(Zr, Ti)O3 (PZT) as a typical ferroelectric material and applying X-ray photoelectron spectroscopy (XPS), we briefly review the interface formation and barrier heights at the inter- faces between PZT and electrodes made of various metals or conductive oxides. Polarization dependence of the Schottky barrier height at a ferroelectric/electrode interface is also directly observed using XPS.