As luminescence applications of colloidal semiconductor nanocrystals push toward higher excitation flux conditions, there is an increased need to both understand and potentially control emission from multiexciton states. We develop a spectrally resolved correlation method to study the triply excited state that enables direct measurements of the recombination pathway for the triexciton, rather than relying on indirect extraction of rates. We demonstrate that, for core–shell CdSe–CdS nanocrystals, triexciton emission arises exclusively from the band-edge S-like state. Time-dependent density functional theory and extended particle-in-a-sphere calculations demonstrate that reduced carrier overlap induced by the core–shell heterostructure can account for the lack of emission observed from the P-like state. These results provide a potential avenue for the control of nanocrystal luminescence, where core–shell heterostructures can be leveraged to control carrier separation and therefore maintain emission color purity over a broader range of excitation fluxes.