The photoelectron spectrum of the 7,7,8,8-tetracyanoquinodimethane (TCNQ) radical anion has been measured at 3.1 eV. Additionally, the ultrafast relaxation dynamics of the first excited state (1(2)B(3u)) of TCNQ(-) have been studied using time-resolved photoelectron spectroscopy, which reveals that it undergoes internal conversion back to the ground state ((2)B(2g)) with an associated lifetime of 650 fs and shows evidence of coherent nuclear motion.