We study the importance of inter-site coherences and quantum interference effects in the X-ray absorption spectroscopy (XAS) of mixed-valent systems. We demonstrate its importance, first for a simple diatomic mixed-valent molecule to elucidate the physics involved and finally for mixed-valent Ti oxides, using a model calculation including full spin and orbital multiplicities. Our calculations demonstrate the inefficacy of conventional approaches of describing the XAS from mixed-valent systems as incoherent combinations of XAS from the pure-valent end members and that multiplets forbidden in the single-site approximation can be effectively reached within a multi-site description. These conclusions play an important role in the interpretation of XAS and resonant X-ray scattering (RXS) in terms of the electronic structure of strongly correlated systems. Copyright {\textcopyright} EPLA, 2011.