Effects of substituents on the lengths of the central C–C single bond in the butterfly-shaped anthracene photodimers (1)–(7) and lepidopterenes (8) are studied. X-Ray analysis of the photodimer (10) of 9,10-difluoroanthracene gave a C(9)–C(10′) bond length of 1.631 (3)Å. An attempt to re-determine molecular structure of the photoisomer (5) of [2.2](9,10) anthracenophane (12) by neutron diffraction analysis is also reported [C(9)–C(10′): obs. 1.64(1), calc. 1.63(1)Å]. The D₂ structure that had been proposed for the minimum-energy conformation of (5) is questioned and the D_2h symmetric conformation is suggested on the basis of the diffraction results and MNDO calculations. The experimentally determined distances of the long central C–C bonds in these butterfly compounds including dianthronyl (9) are well reproduced by MNDO calculations with a standard deviation of 0.013 Å. Small but significant further elongation of the central C–C bond by up to 0.07 Å resulting from annulation of cyclobutane or cyclopentane ring in anthracene photodimers and from remote chlorine substitution in lepidopterene are interpreted in terms of the increased π→σ* orbital interaction.