A photofragment excitation spectrum of aniline cation, C6H5NH2+, was measured in the range of 450-400 nm by ion-trap mass spectrometry. The trapped cations exposed to a nanosecond laser field (I approximate to 1 MW/cm(2), Deltat approximate to 10 ns) absorbed two photons and dissociated into C5H6+ efficiently in the 427-417 nm range. From a comparison with the photoelectron spectrum of neutral aniline, it is identified that the photodissociation of aniline cation into C5H6+ proceeds via the second electronically excited ((B) over tilde B-2(1)) state. (C) 2004 Elsevier B.V. All rights reserved.