The effects of ethynyl substitution on cyclobutadiene are explored via density functional theory and coupled duster calculations: The computed singlet-triplet gaps indicate a monotonic dependence on the degree of ethynyl substitution, which differentially stabilizes the triplet relative to the singlet ground state and reduces the gap. A series of isodesmic, homodesmotic, and hyperhomodesmotic equations are employed to quantify the stabilization upon ethynyl substitution. Analyses that rely on a simple isodesmic equation and/or B3LYP/6-31G(d) values are found to be problematic. Analyses that rely on homodesmotic or hyperhomodesmotic equations, in conjunction with CCSD/cc-pVDZ values, are more robust. Using a hyperhomodesmotic equation to assess the stabilization enthalpies of tetra-substituted singlet cyclobutadienes, our analysis predicts tetramethylcyclobutadiene (Delta H(rxn)(0) = -17.3 kcal/mol) to be more stable than tetraethynylcyclobutadiene (Delta H(rxn)(0) = -11.7 kcal/mol), which, in turn, is substantially more stable than tetracyanocyclobutadiene (Delta H(rxn)(0) = +12.7 kcal/mol).