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Biindenylidene isomers are components of pyrolysis oils. The mass spectra were recorded and the fragmentation of the following biindenylidene isomers: (E)-2,3,2,3-tetrahydro-[1,1]biindenylidene, (Z)-2,3,2,3-tetrahydro-[1,1]biindenylidene, 1,3,1,3-tetrahydro-[2,2]biindenylidene and 2,3,1,3-tetrahydro-[1,2]biindenylidene, as well as of spiro[1,1a,6,6a-tetrahydrocyclopropa[a]indene-1,1-2,3-dihydro-1H-indene] is discussed.