Singlet α-methylbenzylidenecarbene has been detected and characterized for the first time by femtosecond transient absorption (fs-TA) spectroscopy. The carbene was generated by photolysis of the hydrocarbon precursor, 1-(1-phenylethylidene)-1a,9b-dihydro-1 H-cyclopropa[ l]-phenanthrene, in acetonitrile. The photolysis initially forms the singlet excited state of the precursor which then extrudes α-methylbenzylidenecarbene in 4.0 ps. The decay of α-methylbenzylidenecarbene, which was previously shown to rearrange into phenylpropyne by a 1,2-phenyl shift, occurred over 13.3 ps. Computed spectra at the TD-B3LYP/6-311+G** level of theory are consistent with the experimental observations. CASSCF(10,10)/6-311+G** calculations, using one of the carbene conformers as a model, indicated that the reference wave function is dominated by a closed-shell description.