We present improved virtual orbital (IVO) complete active space (CAS) configuration interaction (IVO-CASCI) and IVO-CASCI-based multireference Møller-Plesset perturbation theory (MRMPPT) calculations with an aim to elucidate the electronic structure of tetramethyleneethane (TME) in its lowest singlet and triplet state and to quantify their order and extent of splitting. The potential surfaces of singlet and triplet states for the twisting of TME are also studied. We found that the triplet state is higher in energy than the singlet one in the whole range of twisting angles with the energy gap minimum at a twisting angle of about 45°. Harmonic vibrational frequencies of TME have also been calculated for both the states. We also report the ground to first excited triplet state transition energies. Our results are analyzed with respect to the results available in the literature to illustrate the efficacy of our methods employed. We also demonstrate that the spin character of the ground state of disjoint, TME-like diradicals can be manipulated by using appropriate selection of annulenic spacer to separate the allyl groups of TME.