The interactions between a dicationic gemini surfactant with a six-hydrocarbon spacer (1,2-bis(dodecyldimethyl-ammonio)hexane dibromide, C12C6C12Br2) and anionic polyelectrolyte DNA or sodium(polystyrene sulfonate) (NaPSS) at the air/solution interface have been studied and compared using neutron reflectometry together with surface tension. In the presence of the dichained cationic gemini surfactant, DNA and NaPSS display very different adsorption behaviors. The DNA/gemini mixtures show adsorption behavior very similar to that of DNA/C(12)TAB mixtures, with enhanced surfactant adsorption at low concentrations and thick structured layers at higher concentrations. However, for the NaPSS/gemini mixtures the amount of gemini at the surface is reduced relative to that in the absence of NaPSS at concentrations below the cmc. These differences in adsorption behavior are attributed to differences in the molecular structure and flexibility of the two polyanions. NaPSS is relatively hydrophobic and flexible enough to form bulk-phase polymer-micelle complexes with the gemini surfactant at low surfactant concentrations, whereas the adsorption of surface complexes is much less favorable because the dications on the gemini would require adjacent bulky pendant charges on the NaPSS to be oriented toward the surface. This would force the NaPSS to bend significantly whereas it is more favorable for the NaPSS to adopt an extended conformation at the surface. Thus, surfactant is actually removed from the surface to form bulk-phase complexes. In contrast with NaPSS, DNA has a far more rigid structure, and the charges on the backbone are at fixed intervals, factors that make the formation of surface DNA-monomer complexes much more favorable than bulk-phase DNA-micelle complexes. Finally, a short-chain sample of NaPSS consisting of only five to six segments adsorbs very strongly at the surface with the gemini to form more extensive layered structures than have previously been observed, consisting of approximately five sublayers.