The curved plots of (carbene adduct)/(carbene-rearrangement product) versus carbene trapping agent, tetramethylene [TME], reported with benzylchlorodiazirine 1 have been reproduced. However, with the use of a non-nitrogenous precursor, plots of this type are approximately linear over the range of [TME] employed. Thus, any complex formed between benzylchlorocarbene and TME must collapse to form cyclopropane faster then it can fragment with rearrangement to beta-chlorostyrene and TME. Diazirine 1 does photoisomerize to diazo compound 7, but this process is inefficient (phi = 0.075) and is not likely to be responsible for the curvature in plots of adduct/styrene versus [TME] observed with the diazirine precursor. Thus, the second, noncarbene, pathway to beta-chlorostyrene is neither a carbene-olefin complex nor a diazo intermediate. It is proposed that the second pathway involves a rearrangement in the excited stale of the diazirine, although other explanations cannot be discarded.