The processes of singlet fission and triplet fusion could allow state-of-the-art photovoltaic devices to surpass the Shockley–Queisser limit by optimizing the utilized solar spectrum by reducing thermal relaxation and inaccessible sub-bandgap photons, respectively. Triplet fusion demands precise control of the spin-triplet state population, and requires a sensitizer to efficiently populate the triplet state of an acceptor molecule. In this perspective, we highlight the established field of sensitized upconversion and further examine alternative triplet sensitization routes, including the possibility of bulk solid-state semiconductors as triplet sensitizers, which provide a new avenue for charge transfer-based triplet sensitization rather than excitonic triplet energy transfer.