The molecular structures of ethyrylbenzene and s-triethynylbenzene have been accurately determined by gas-phase electron diffraction and ab initio/DFT MO calculations and are compared to that of p-diethynylbenzene from a previous study [Domenicano, A.; Arcadi, A.; Ramondo, F.; Campanelli, A. R.; Portalone, G.; Schultz, G.; Hargittai, I .J. Phys. Chem. 1996, 100, 14625]. Although the equilibrium structures of the three molecules have C-2v, D-3h, and D-2h symmetry, respectively, the corresponding average structures in the gaseous phase are best described by nonplanar models of C-s, C-3v, and C-2v symmetry, respectively. The lowering of symmetry is due to the large-amplitude motions of the substituents out of the plane of the benzene ring. The use of nonplanar models in the electron diffraction analysis yields ring angles consistent with those from MO calculations. The molecular structure of ethynylbenzene reported from microwave spectroscopy studies is shown to be inaccurate in the ipso region of the benzene ring. The variations of the ring C-C bonds and C-C-C angles in p-diethynylbenzene and s-triethynylbenzene are well interpreted as arising from the superposition of independent effects from each substituent. In particular, experiments and calculations consistently show that the mean length of the ring C-C bonds increases by about 0.002 angstrom per ethynyl group. MO calculations at different levels of theory indicate that though the length of the C equivalent to C bond of the ethynyl group is unaffected by the pattern of substitution, the C-ipso-C-ethynyl bonds in p-diethynylbenzene are 0.001-0.002 A shorter than the corresponding bonds in ethynylbenzene and s-triethynylbenzene. This small effect is attributed to conjugation of the two substituents through the benzene ring. Comparison of experimental and MO results shows that the differences between the lengths of the C-ipso-C-ethynyl and C-ipso-C-ortho bonds in the three molecules, 0.023-0.027 angstrom, are correctly computed at the MP2 and B3LYP levels of theory but are overestimated by a factor of 2 when calculated at the HF level.