We have investigated the optical properties of colloidal seed-grown CdSe (seed)/CdTe (arms) nanotetrapods both experimentally and computationally. The tetrapods exhibit a type-II transition arising from electrons localized in the CdSe seed region and holes delocalized in the CdTe arms, along with a residual type-I recombination in long-arm tetrapods. Experiments and theory helped to identify the origin of both types of transitions and their size dependence. In particular, time-resolved experiments performed at 10 K evidenced a size-dependent, long living type-II radiative emission arising from the peculiar electron–hole wave function localization. Temperature-dependent photoluminescence (PL) studies indicate that, at high temperature (>150 K), the main process limiting the PL quantum efficiency of the type-I PL is thermal escape of the charge carriers through efficient exciton-optical phonon coupling. The type-II …