Single and multiple photon ionization photoelectron spectroscopy of triethylamine (TEA) was studied using a newly developed high-resolution electron spectrometer which utilizes position sensitive detection. The adiabatic ionization potential of TEA was accurately determined using both single (7.47+/-0.04 eV) and multiphoton (7.53+/-0.10 eV) ionization photoelectron spectroscopy. Although excitation to both the S-1 and S-2 states can occur, multiphoton ionization always occurs out of the S, state. When the cation dissociates, the distribution of photoelectron energies similarly reflects this partitioning between S-1 and S-2.