AbstractThe reduction of pyrene with sodium in aprotic diethyl ether allows to crystallize the extremely air‐sensitive radical ion pair pyrene‐sodium‐diethylether. The single‐crystal structure determination at 130 K shows that each sodium counter cation, solvated by one diethyl‐ether molecule, is η3‐ and η6‐coordinated to one of the short‐axis six‐membered rings of two pyrene radical anions. The resulting dibenzene‐sodium sandwiches form a string, in which the hydrocarbon planes are canted to each other by 62°. In the pyrene radical‐anion skeleton, no distortion due to its negative charge can be detected relative to that of the neutral molecule. From the temperature‐dependent signal multiplets of preceding ESR investigations, the solvent‐separated pyrene radical anion as well as two different contact radical‐ion pairs had been identified and their structures in solution approximated by potential‐energy estimates. Referring to the recently discovered long‐axis Na⊕ contact ion pair polymorph, crystallized at lower temperatures, the structure reported here represents the second and probably thermodynamically more stable one. Both the ESR and the structural results provide some insight into the multidimensional networks of equilibria in aprotic solution, which are activated by alkali‐metal redu