Morphotropic phase boundary (MPB), which is a special boundary that separates two or multiple different phases in the phase diagram of some ferroelectric ceramics, is an important concept in identifying physics that includes piezoelectric responses. MPB, which had not been discovered in organic materials until recently, was discovered in poly(vinylidene fluoride-co- trifluoroethylene (P(VDF-TrFE)), resulting from a molecular approach. The piezoelectric coefficient of P(VDF-TrFE) in this MPB region was achieved up to -63.5 pC N^-1, which is about two times as large as the conventional value of -30 pC N^-1 of P(VDF-TrFE). An order-disorder arrangement greatly affects the rise of the piezoelectric effect and the ferroelectric, paraelectric and relaxor ferroelectric of P(VDF-TrFE), so the arrangement and shape of the polymer chain is important. In this review, we investigate the origin of negative longitudinal piezoelectric coefficients of piezoelectric polymers, which is definitely opposite to those of common piezoelectric ceramics. In addition to the mainly discussed issue about MPB behaviors of ferroelectric polymers, we also introduce the consideration about polymer chirality resulting in relaxor ferroelectric properties. When the physics of ferroelectric polymers is unveiled, we can improve the piezoelectric and pyroelectric properties of ferroelectric polymers and contribute to the development of next-generation sensor, energy, transducer and actuator applications.