The S1 (2 1 Ag-) state is an optically dark state of natural and synthetic pi-conjugated materials that can play a critical role in optoelectronic processes such as, energy harvesting, photoprotection and singlet fission. Despite this widespread importance, direct experimental characterisations of the electronic structure of the S1 (2 1 Ag-) wavefunction have remained scarce and uncertain, although advanced theory predicts it to have a rich multi-excitonic character. Here, studying an archetypal polymer, polydiacetylene, and carotenoids, we experimentally demonstrate that S1 (2 1 Ag-) is a superposition state with strong contributions from spin-entangled pairs of triplet excitons (1 (TT)). We further show that optical manipulation of the S1 (2 1 Ag-) wavefunction using triplet absorption transitions allows selective projection of the 1 (TT) component into a manifold of spatially separated triplet-pairs with lifetimes enhanced by up to one order of magnitude and whose yield is strongly dependent on the level of interchromophore coupling. Our results provide a unified picture of 2 1 Agstates in pi-conjugated materials and open new routes to exploit their dynamics in singlet fission, photobiology and for the generation of entangled (spin-1) particles for molecular quantum technologies.