The measured surface tension of a binary liquid is found to depend strongly on the constituents of the adjacent vapor and on whether equilibrium has been achieved, giving insight into the complex interfacial configuration. This dependence is quantified by three techniques that offer complementary insights: surface tension measurements with a constrained sessile drop surrounded by different vapors, surface tension measurements by surface light scattering spectroscopy in a sealed cell at equilibrium, and molecular dynamics simulations of the equilibrium surface tension and excess surface concentration. Ensuring homogeneity of the binary liquid, which is essential for surface light scattering, was found to be nontrivial and was assured by high-sensitivity Schlieren imaging. Two pairs of liquids, n-pentane with 2-methylpentane and n-pentane with n-hexane, were investigated. The first pair was motivated by the observed improvement in the effectiveness of binary fluids versus a single constituent in wickless heat pipes studied in microgravity. The second pair was used for comparison. Experimental evaluation of different volume fractions of the two liquids showed strong dependence of surface tension on the relative concentration of different molecules near the interfacial region. For the above pairs of liquids, which appear to form ideal mixtures in bulk, we present sufficiently precise surface tension measurements to indicate unexpectedly complex behaviors at interfaces.