Zero kinetic electron energy photodetachment spectroscopy of I(-)·H(2)O and I(-)·D(2)O has been performed from 27 660 to 28 500 cm(-1) and from 27 660 to 35 900 cm(-1), respectively. The I(-)·D(2)O spectral data and theoretical studies resulted in a reassignment of earlier anion-ZEKE spectra of iodide water ( Bässmann , C. ; et al. Int. J. Mass Spectrom. Ion Processes 1996 , 159 , 153 ). In opposite to the I(-)·H(2)O, the I(-)·D(2)O spectrum reveals a regular progression of the iodine-water van der Waals stretching mode and a short progression of even quanta of the van der Waals rocking mode. A rough estimation delivers dissociation thresholds of the anionic and of the lower and the upper spin-orbit component of the neutral van der Waals complex. A high resolution ZEKE spectrum of the van der Waals stretching mode (v = 1) reveals significant fine structure, which is found again in a former photodissociation spectrum of the anionic complex ( Ayotte , P. ; et al. J. Phys. Chem. A 1998 , 102 , 3067 ). Our assignments are supported by theoretical calculations of molecular structures and vibrational motions. Vibrational frequencies and isotope effects are reproduced very satisfyingly by these calculations.