Several singlet and triplet potential energy surfaces (PES) for the Bergman cyclization of cis-1,5-hexadiyne-3-ene (1a) have been computed by UDFT, CI, CASCI, CASSCF, and CASMP2 methods. It is found that the first six excited states of la can be qualitatively described as linear combinations of the configurations of weakly interacting ethylene and acetylene units. Although the symmetry relaxation from C-2 nu to C-2 makes cyclization of the 1(3)B state Woodward-Hoffmann allowed, it also increases the probability of competing cis-trans isomerization. Hydrogen atom abstraction is another plausible pathway because the terminal alkyne carbons possess a large radical character. In view of the competing processes, we conclude that the Bergman cyclization along the 1(3)B path is unlikely despite its exothermicity (DeltaH(rxn)(CASMP2) = -42 kcal/mol). Calculations on cyclic analogues of la lead to similar conclusions. A less exothermic, but more plausible pathway for photochemical cyclization lies on the 2(1)A PES (DeltaH(rxn)(CASMP2) = -18 kcal/mol). Compared to the 1(1)A(1) and 1(3)B states, the 2(1)A state has less in-plane electron repulsion which may facilitate cyclization. The resulting p-benzyne intermediate has an unusual electronic structure combining singlet carbene and open-shell diradical features. Deactivation of the 2(1)A state of 1a is a competing pathway.