Triplet 4-methylbenzenesulfonylnitrene 3 was studied by solution phase laser flash photolysis, low-temperature absorption spectroscopy, and low-temperature EPR spectroscopy. Upon laser flash photolysis of 4-methylbenzenesulfonyl azide 1 in ethanol, absorption maxima were observed at 325 and 460 nm while in cyclohexane, a single maximum was observed at 310 nm. The short-wavelength absorptions were assigned to the triplet nitrene. There was no evidence that hydroxylic solvents catalyzed intersystem crossing from the singlet to the triplet state of 3. After irradiation of 1 in an EPA glass at 77 K, a band at 313 nm was observed. The zero-field splitting parameters from the EPR spectrum of the nitrene in an EPA glass at 77 K were D/hc = 1.471 cm(-1) and E/hc = 0 cm(-1). Remarkably, 3 was not stable at 77 K in EPA. Irradiation of 1 also produced a second nitrene species, possibly (4-methylphenyl)nitrene, with D/hc = 0.9840 cm(-1) and E/hc = 0 cm(-1). The decay of the 325 nm transient was first order in ethanol (tau = 8.96 +/- 0.48 mu s), methanol (tau = 8.18 +/- 0.08 mu s), and methanol-d(4) (tau = 8.02 +/- 1.76 mu s).