The chemical reduction of a pyracylene-hexa-peri-hexabenzocoronene-(HBC)-fused nanographene TPP was investigated with K and Rb metals to reveal its multi-electron acceptor abilities. The in situ reaction of TPP with the above alkali metals, monitored by UV-vis-NIR and ¹H NMR spectroscopy, evidenced the stepwise reduction process. The use of different solvents and secondary ligands enabled isolation of single crystals of three different reduced states of TPP with 1, 2, and 3 electrons added …