The concept of charge-polarization coupling in the ferroelectric copolymer PVDF–TrFE (poly[vinylidene fluoride-co-trifluoroethylene]) has been revisited by employing high resolution (<50 nm) pyroelectric depth profiling (LIMM). By virtue of probing the pyroelectric activity over the film thickness in the presence of a variable, external electrical field, the local ferroelectric response and spatially resolved hysteresis could be obtained. A large asymmetry was found between the positive and negative electrode–polymer interface. Differences in amplitude of polarization, contribution of interface charges and length scale of the polarization-free zone near the electrodes suggest a higher availability of compensation charges at the negative electrode that finally stabilize the local polarization. The resulting asymmetries in the polarization distribution are hence attributed to excess charges as a result of electron injection as a specific charge generation mechanism at the negative electrode.