p-(Dimethylamino)phenyl pentazole, DMAP-N-5 (DMAP = Me2N-C6H4), was characterized by picosecond transient infrared spectroscopy and infrared spectroelectrochemistry. Femtosecond laser excitation at 310 or 330 nm produces the DMAP-N-5 (S-1) excited state, part of which returns to the ground state (tau = 82 +/- 4 ps), while DMAP-N and DMAP-N-3 (S-0) are generated as double and single N-2-loss photoproducts with eta approximate to 0.14. The lifetime of DMAP-N-5 (S-1) is temperature and solvent dependent. [DMAP-N-3](+) is produced from DMAP-N-5 in a quasireversible, one-electron oxidation process (E-1/2 = +0.67 V). Control experiments with DMAP-N-3 support the findings. DFT B3LYP/6-311G** calculations were used to identify DMAP-N-5 (S-1), DMAP-N-3(+), and DMAP-N in the infrared spectra. Both DMAP-N-5 (S-1) and [DMAP-N-5](+) have a weakened N-5 ring structure.