X-ray diffraction was used to probe the structural changes associated with the conversion of the paraelectric phase to the ferroelectric phase that results from the application of a large external electric field. The samples under study are ultrathin (150 to 250 Å) Langmuir-Blodgett films of the copolymer vinylidene fluoride (70%) with trifluoroethylene (30%) deposited on aluminum-coated silicon. Theta-2theta X-ray diffraction was used to measure the change in inter-layer spacing perpendicular to the film surface. Upon heating at zero external electric field, the crystalline films undergo a structural phase transition, at 100± 5°C, from the all-trans ferroelectric phase to the trans-gauche paraelectric phase. [1,2] Above the phase transition temperature, the non-polar paraelectric phase can be converted back to the polar ferroelectric phase, in a smooth continuous process, using a large external electric field (∼1 GV/m). For example, at 100° C the ferroelectric phase first appears above 0.2 GV/m and increases steadily in proportion while the paraelectric phase decreases until complete conversion to the ferroelectric phase is achieved at approximately 0.6 GV/m.