Vinylidene fluoride (VDF) oligomers with uniform molecular weights were separated successfully by using supercritical fluid chromatography, and the crystal structures were determined by X-ray analysis of the single crystals. Although the chemical formulas of these oligomer components had not been known clearly, the X-ray structure analysis gave us the following results: CF(CF 3)2-(CH2-CF2)n-I with n ) 6-12. The oligomer chains were found to form a layer structure, in which the chains are tilted slightly from the normal to the layer plane. The chain conformation of the oligomers, when crystallized from ethanol solutions, was a repetition of TGTG h , essentially the same with that of poly-(vinylidene fluoride) crystal form II. The packing structure of central VDF sequence parts was also found to be the same with that of form II: the chains are packed in an antiparallel mode with respect to the chain direction as well as the direction of CF 2 dipoles. A series of oligomers were found to show a variety of crystal modifications depending on the sample preparation conditions, as seen from the infrared spectral patterns.