BaTiO₃ is a prototypical ferroelectric material with spontaneous polarization resulting from atomic displacement in the unit cell. We employ the X-ray standing wave technique to probe Ba and Ti atomic positions within the unit cells near the surface. This is particularly relevant for applications of ferroelectric materials in chemical reactions, where the polarization near the surface plays a crucial role. We also performed time-resolved Second Harmonic Generation experiments and demonstrated up to 40% reversible reduction of the polarization within 120 fs, with a recovery time of several 10s of ps. Finally, time-resolved X-ray diffraction were performed to study the lattice dynamics upon pumping with 266 nm laser.