We present a novel method to determine the spectral ionization probability of sputtered species as a function of their emission velocity or energy. The technique is based on detection of neutral and ionic species in a reflectron time-of-flight mass spectrometer under otherwise identical experimental conditions. Using a pulsed ion extraction scheme in combination with sufficiently short primary ion pulses, the spectral ionization probability alpha(+)(v) can be determined without knowledge of possible energy discrimination effects in instrument transmission. Comparing the measured ionization probability with theoretical predictions, we find that none of the prevailing ionization models is capable of describing the experimental data over the whole velocity range studied. (c) 2006 Elsevier B.V. All rights reserved.