Fast radiative cooling of anthracene was observed in a compact electrostatic storage ring by probing the evolution of the internal energy distribution of a stored (C(14)H(10))(+) molecular ensemble via laser excitation. We have measured the mean radiative decay rate to be about 120 to 250 s(-1) for internal energies in the range from 6.6 to 6.8 eV. Such a high decay rate is 2 orders of magnitude larger than the infrared emission cooling rate expected for vibrational transitions. It is attributed to fluorescence from thermally excited electrons. This fast cooling mechanism may have important implications in astrophysics concerning the lifetime and the critical size of polycyclic aromatic hydrocarbons in interstellar conditions.