Through the use of a potentially removable tether, a heavily substituted 10b,10c-dimethyl-10b,10c-dihydropyrene (DMDHP), 20, was synthesized exclusively as the cis-isomer. It exists as the major component (20:1) in an equilibrium with its valence isomer syn-[2.2]metacyclophanediene 19. An X-ray crystal structure determination of 20, a cis-(2,7)-10b,10c-dihydropyrenophane, provided the first experimental. measurements of the cis-DMDHP skeleton. The observed bond alternation in the [14]annulene was found to be larger than that of the corresponding trans-DMDHP framework. Prior MMPI calculations, on which previous discussion of the structure of the cis-DMDHP system had been based, are in very good agreement with the experimental results. Our own DFT calculations predict a more symmetric and more bond equalized structure than was observed in 20.