This review focuses on the study of excited state photoionization dynamics for the characterization of the spectroscopy and decay dynamics of low-lying neutral excited states as well as autoionizing states of small polyatomic molecules. The review emphasizes the use of double-resonance excitation techniques to prepare selectively excited states of interest, and the use of energy dispersive photoelectron spectroscopy to characterize the states of interest through their photoionization dynamics. (C) 2004 Elsevier Ltd. All rights reserved.