Random copolymers of methyl methacrylate (MMA) and sermifluorinated methacrylate (sfMA), with constant side chain length (H10F10), as comonomers and various sfMA molar contents were studied by Dielectric Relaxation Spectroscopy (DRS) technique with respect to their phase transitions and molecular dynamics. DRS technique was proven a suitable technique for the detection of the phase transitions that take place in the systems under investigation, as it follows from the comparison with Differential Scanning Calorimetry (DSC) technique, which is traditionally used. Regarding molecular mobility, molecular motions of both the main chain and the sf side chains were followed, while different dynamics was recorded depending on the structure of the copolymers.