The reduction of 7,7,8,8-tetracyanoquinodimethane (TCNQ) generates a π radical anion, TCNQ-, that dimerizes in methanol solution. This dimer ([TCNQ]2 2-) exhibits a charge-transfer absorption peak at 620 nm and will disproportionate to give TCNQ and TCNQ2- in response to excitation within this charge-transfer band. The present study examined the electronic dynamics of [TCNQ]2 2- disproportionation. The disproportionation was found to proceed in two steps. Electron transfer, representing the first step, occurred within the 10 fs pulse window, followed by the actual dissociation, within 350 fs. The emission lifetime of the singlet excited state of TCNQ2- was estimated to be 900 fs.