Two types of anion states are shown to coexist in nanometer-scale polyacene cluster anions. Naphthalene and anthracene nanoclusters having a single excess electron were produced in the gas-phase. Photoelectron spectra of size-selected cluster anions containing 2 to 100 molecules revealed that rigid "crystal-like" cluster anions emerge, greater than similar to2 nanometers in size, and coexist with the "disordered" cluster anion in which the surrounding neutral molecules are reorganizing around the charge core. These two anion states appear to be correlated to negative polaronic states formed in the corresponding crystals. (C) 2004 American Institute of Physics.