A study employing picosecond and subpicosecond excitation in a mass and photoelectron spectrometer is reported for the 7-azaindole (7-AI) dimers, reactive and unreactive. The 7-AI photoelectron spectrum is structured and has a sharp ionisation threshold at 8.17 eV above the neutral ground electronic state. The reactive dimer ionisation threshold was measured as 7.19 eV. The excited-state lifetime of the reactive dimer was measured by a technique that monitors the ionisation signal as a function of pulse duration. 1 + 1 resonance ionisation photoelectron spectra were recorded using 0.8 ps and 5 ps pulses. Our results indicate a lifetime substantially less than a picosecond, however, consistent with recent real time studies. Advantages of the method are discussed.