Piezoelectricity and pyroelectricity, traditionally encountered in certain single crystals and ceramics, have now also been documented in a number of polymers. Recently, one such polymer—poly(vinylidene fluoride)—and some of its copolymers have been shown to be ferroelectric as well. The extraordinary molecular and supermolecular structural requirements for ferroelectric behavior in polymers are discussed in detail, with particular emphasis on poly(vinylidene fluoride). Piezoelectric, pyroelectric, and ferroelectric properties are also briefly reviewed, as are some promising applications of such polymers.