An attempt has been made to redetermine the enthalpy and entropy of formation of the charge-transfer complex between tetracyanoethylene and biphenylene in dichloromethane solution from measurements of the equilibrium constant at different temperatures. The results obtained under conditions where biphenylene is in excess differ from those previously published in which tetracyanoethylene was in excess. It is argued that the optimum condition for determining equilibrium constants of a 1:1 complex is when the reactants are mixed in solution in this ratio. Determinations under this condition yield ΔH = −2.6 kcal mole−1and ΔS = −4.1 e.u.The energies of the intermolecular charge-transfer transitions of biphenylene with several different acceptors suggest that the ionization potential of biphenylene is ~7.4 eV.