The origin and chain length evolution of the stat:ic third-order polarizability, gamma, are discussed in polyenes up to C80H82 Via a local analysis of atomic pi-orbital electric field-induced polarizations, i.e., of gamma charges and their moments. This conceptually and computationally simple approach allows one to obtain a visual representation of the local contributions to gamma.The patterns of these local contributions are observed to change qualitatively as a function of chain length; the end parts of the molecule dominate the third-order response at moderate chain lengths, while the contributions from the inner section are responsible for the slow chain-length saturation.