Ferroelectric crystalline copolymer films of vinylidene fluoride with trifluoroethylene (70%:30%) strongly interact with the dipoles of adsorbed and absorbed water molecules. This interaction can be probed with laser-assisted thermal desorption techniques. The UV light enhancement of water desorption is strongly light polarization dependent. The electronic structure of the ferroelectric copolymer films of vinylidene fluoride with trifluoroethylene films is locally altered with incident UV radiation suggesting metastable excited states that may involve dipole reorientation.