We explore the dynamic interaction of charge carriers between band-edge states and sub-band trap states in PbS quantum dot (QD) solids using time-resolved spectroscopy. In monodisperse arrays of 4- to 5-nm diameter PbS QDs, we observe an optically active trap state ∼100–200 meV below the band edge that occurs at a frequency of 1 in ∼2,500 QDs. Uncoupled QD solids with oleic acid ligands show trap-to-ground-state recombination that resembles Auger recombination. In electronically coupled QD solids, we observe entropically driven uphill thermalization of trapped charge carriers from the trap state to the band edge via two distinct mechanisms: Auger-assisted charge transfer (∼35 ps) and thermally activated hopping (∼500 ps). Photophysical characterization combined with atomistic simulations and high-resolution electron microscopy suggest that these states arise from epitaxially fused pairs of QDs rather than electron or hole traps at the QD surface, offering new strategies for improving the optoelectronic performance of QD materials.Department of Energy (DOE), Office of Basic Energy Sciences (Awards DE-SC0010538,DE-SC0019345)National Science Foundation (Awards 1452857 and 1122374)