Ab initio molecular orbital calculations demonstrate that ionizing alkyl nitriles produces a dramatic geometry change involving lengthening of a C-CH2CN bond, The experimental determination of the adiabatic ionization energy of these species is thus very difficult. In addition, there are generally low barriers for 1,2-H shift reactions in the molecular ions leading to RCHCHN+center dot and RCHCNH+center dot isomers, which makes generating pure ionized alkyl nitrile in a mass spectrometer a challenge. Threshold photoelectron spectroscopy and threshold photoelecton photoion coincidence spectroscopy were employed to Study the ionization and dissociation of two alkyl nitriles, in particular, pentanenitrile and 2,2-dimethylpropanenitrile. Threshold ionization is shown to result not in the respective molecular ions, but rather in isomeric forms, resulting in dissociation thresholds that lie below the calculated adiabatic ionization energies of the two molecules. Appearance energies for all observed fragment ions are reported and compared to available literature values. Charge separation in the dissociation of doubly ionized 2,2-dimethylpropanenitrile is observed as fragmention time-of-flight peak broadening at high photon on energies.