We have established ferroelectric switching and observed a novel conductance switching phenomenon in ferroelectric polymer films fabricated by the Langmuir–Blodgett technique. The films consist of 10–30 monolayers (ML) of a copolymer of vinylidene fluoride (70%) and trifluoroethylene (30%), exhibiting a first-order ferroelectric phase transition at 70 °C and nearly rectangular ferroelectric and conductance hysteresis at 24 °C. Ferroelectric switching is accompanied by switching of the conductance by three orders of magnitude. A model describing this switching phenomenon is proposed.