Diphenylcarbene (DPC) generated by high-intensity laser photolysis of diphenyldiazomethane rearranges to fluorene (FL) by two distinct mechanisms as revealed by methyl-group labeling. Thus, excimer laser irradiation of p,p'-dimethyldiphenyldiazomethane generates 3,6-dimethylfluorene (3,6-DMF) and 2,7-dimethylfluorene (2,7-DMF), which were identified by fluorescence measurements as well as GC-MS and comparison with authentic materials. 3,6-DMF corresponds to direct bond formation between ortho positions in DPC, referred to as ortho,ortho' coupling. 2,7-DMF corresponds to a carbene-carbene rearrangement, whereby DPC undergoes ring expansion to phenylcycloheptatetraene (PhCHT) followed by ring contraction to o-biphenylylcarbene (o-BPC), which then cyclizes to FL. The carbene-carbene rearrangement dominates over the ortho,ortho' coupling under all conditions employed. The ortho,ortho' coupling must take place in a higher excited state (most likely S2 or T1) of DPC, because it is not observed at all under thermolysis conditions, where only S1 and T0 are populated. The carbene-carbene rearrangement may take place either in a hot S1 state or more likely in a higher excited state (S2 or T1).