Singlet fission is a process in which a singlet exciton converts into two triplet excitons. To investigate this phenomenon, we synthesized two covalently linked 5-ethynyl-tetracene (ET) dimers with differing degrees of intertetracene overlap: BET-X, with large, cofacial overlap of tetracene Pi-orbitals, and BET-B, with twisted arrangement between tetracenes exhibits less overlap between the tetracene Pi-orbitals. The two compounds were crystallographically characterized and studied by absorption and emission spectroscopy in solution, in PMMA and neat thin films. The results show that singlet fission occurs within 1 ps in an amorphous thin film of BET-B with high efficiency (triplet yield: 154%). In solution and the PMMA matrix the S-1 of BET-B relaxes to a correlated triplet pair (1)(T1T1) on a time scale of 2 ps, which decays to the ground state without forming separated triplets, suggesting that triplet energy transfer from (1)(T1T1) to a nearby chromophore is essential for producing free triplets. In support of this hypothesis, selective excitation of BET-B doped into a thin film of diphenyltetracene (DPT) leads to formation of the (1)(T1T1) state of BET-B, followed by generation of both DPT and BET-B triplets. For the structurally cofacial BET-X, an intermediate forms in <180 fs and returns to the ground state more rapidly than BET-B. First-principles calculations predict a 2 orders of magnitude faster rate of singlet fission to the (1)(T1T1) state in BET-B relative to that of crystalline tetracene, attributing the rate increase to greater coupling between the S1 and (1)(T1T1) states and favorable energetics for formation of the separated triplets.