Debye-type dielectric relaxation has been revealed for the first time and investigated in the ferroelectric phase of ultrathin (15–45 nm) Langmuir-Blodgett (LB) films of vinylidene fluoride and trifluorethylene copolymer P[VDF–TrFE] with a first-order phase transition. The Cole–Cole plot of ε′ and ε″ and the relaxation time τ are investigated in a broad frequency and temperature range. The obtained results reveal a perfect crystalline structure of the ultrathin ferroelectric films.