A covalently tethered dyad containing the azulene (Az) and zinc tetraphenylporphyrin (ZnP) chromophores has been synthesized and its excited-state dynamics investigated, using the tether-substituted monochromophoric species as reference compounds. One photon excitation of the dyad at 270 nm results in selective population of the S-2 state of the azulene moiety, followed by near-quantitative electronic relaxation in the cycle S-2(Az)S2(ZnP)-S,(ZnP)-S-2(Az)-S-0. Energy transfer from the S-2 state of the azulene moiety to the S-2 state of the ZnP moiety is ultrafast (keel > 2 x 10(12) s(-1)) and quantitative. The ZnP(S-2) moiety subsequently undergoes rapid (k(ic) = 3 x 10(11) s(-1)), quantitative internal conversion to its S-1 state. Thereafter, the excitation residing on the S, state of the ZnP is returned to the Az moiety via an efficient (ca. 90%) back S,-S, energy transfer process (k(cct) = 2.8 x 10(9) s(-1)). Ultimately the system returns to the electronic ground state via conical intersection of the azulene S, and So surfaces in ca. 1 ps. The cyclic interchromophoric energy transfer rates are nearly the same in both acetonitrile and cyclohexane, suggesting that the conformation of the tether is similar in both solvents. Forster theory is inadequate in explaining the efficient energy transfer dynamics, and other processes such as the Dexter mechanism must be invoked.