We investigate NCl₃ and the NCl₂ radical by photoelectron-photoion coincidence spectroscopy using synchrotron radiation. The mass selected threshold photoelectron spectrum (ms-TPES) of NCl₃ is broad and unstructured due to the large geometry change. An ionization energy of 9.7±0.1 eV is estimated from the spectrum and supported by computations. NCl₂ is generated by photolysis at 213 nm from NCl₃ and its ms-TPES shows an extended vibrational progression with a 90 meV spacing that is assigned to the symmetric N-Cl stretching mode in the cation. An adiabatic ionization energy of 9.94 ± 0.02 eV is determined.