The title compound, [Li(2)(C(9)H(14)N)(C(16)H(36)P(3))](n), is a by-product of the reaction of [Cp(C(5)H(4)CH(2)CH(2)NMe(2))ZrCl(2)](n) with (t)Bu(2)P-P(SiMe(3))Li in toluene. It is a coordination polymer composed of infinite chains running along [010]. One Li(I) atom is chelated by the cyclo-penta-dienyl ring and and the N atom of the scorpionate ligand and a P atom, whereas the other Li(I) atom is coordinated by the backside of the cyclo-penta-dienyl ring and two P atoms. Both Li(I) atoms adopt a distorted trigonal coordination. The structure was determined from a twinned crystal, but only the data from the main twin component was used. The fraction of components in the crystal was 0.555:0.445 and the twin matrix corresponds to twofold rotation about the c axis (00/00/001).