In this thesis, we present the integration of several spectroscopic techniques, based on synchrotrons, free-electron lasers, and optical lasers, to investigate the surface polarization profile and the transient changes in lattice structure, electronic structure, and ferroelectric polarization in BaTiO3 ferroelectric thin films upon above-bandgap optical excitation. This research employs these spectroscopic methods to study specific properties of a prototypical ferroelectric material, grounded in a comprehensive understanding of its fundamental properties and the operating principles of the methods applied. We hope that the findings of this thesis will not only enhance knowledge about the surface polarization and structural dynamics of ferroelectric thin films, but also serve as a template for future studies to combine different spectroscopic methods to resolve the complex dynamics of other materials relevant for technological applications, such as multiferroics.