Palladium-catalyzed terminal alkyne dimerization, through oxidative homocoupling, is a useful approach to the synthesis of symmetrical 1,4-diynes. Recent investigations have suggested that this reaction might be accomplished in the absence of intentionally added stoichiometric oxidants (to reoxidize Pd(0) to Pd(II)). In this paper, we have fully addressed the question of whether oxygen (or added oxidant) is required to facilitate this process. The presence of a stoichiometric quantity of air (or added oxidant such as I2) is essential for alkyne dimerization.