In previous work from our laboratories we have characterized the molecular motion of phenalenyl in the supercage of cation-exchanged X- and Y-zeolites using continuous wave-electron paramagnetic resonance (CW-EPR) and pulsed-EPR techniques. The trends in activation energies with cation size and Lewis acidity and in EPR line widths provided circumstantial evidence for a weak covalent interaction between the neutral phenalenyl alpha-system and the cations. This work on phenalenyl and alkali metal cations in solution provides Li-7 nuclear magnetic resonance (NMR) and CW-EPR spectroscopic evidence for this type of interaction. Moreover, to our knowledge it is the first example of a neutral radical-alkali metal ion complex in solution. In rigorously dried alcohol solutions this interaction results in the formation of a complex between neutral phenalenyl and Li+ or Na+, which is in equilibrium with solvated phenalenyl and the respective cation. The forward and reverse rates for this equilibrium for Li+ and phenalenyl in methanol allow for an analysis of Li-7 NMR data acquired at 320 K in the fast exchange limit, which yields an equilibrium constant of 29 +/- 4 M-1. Analysis of the CW-EPR data for Na+ and phenalenyl in methanol at 295 K in the slow exchange limit produces an isotropic Na hyperfine frequency for the phenalenyl-Na+ complex of 4.2 +/- 0.1 MHz. This hyperfine frequency reflects a Fermi contact with the Na nucleus of ca. 0.5% of the nonbonding pi-electron spin density from phenalenyl.