The four Galilean satellites are thought to harbor one or even two global internal liquid layers beneath their surface layer. The iron core of Io and Ganymede is most likely (partially) liquid and also the core of Europa may be liquid. Furthermore, there are strong indications for the existence of a subsurface ocean in Europa, Ganymede, and Callisto. Here, we investigate whether libration observations can be used to prove the existence of these liquid layers and to constrain the thickness of the overlying solid layers. For Io, the presence of a small liquid core increases the libration of the mantle by a few percent with respect to an entirely solid Io and mantle libration observations could be used to determine the mantle thickness with a precision of several tens of kilometers given that the libration amplitude can be measured with a precision of 1 m. For Europa, Ganymede, and Callisto, the presence of a water ocean close to the surface increases by at least an order of magnitude the ice shell libration amplitude with respect to an entirely solid satellite. The shell libration depends essentially on the shell thickness and to a minor extent on the density difference between the ocean and the ice shell. The possible presence of a liquid core inside Europa and Ganymede has no noticeable influence on their shell libration. For a precision of several meters on the libration measurements, in agreement with the expected accuracy with the NASA/ESA EJSM orbiter mission to Europa and Ganymede, an error on the shell thickness of a few tens kilometers is expected. Therefore, libration measurements can be used to detect liquid layers such as Io's core or water subsurface oceans in Europa, Ganymede, and Callisto and to constrain the thickness of the overlying solid surface layers.