The mechanism of complex formation between surfactants and polyelectrolytes with the same charge on the water surface was investigated using molecular dynamics simulations and phase-sensitive sum-frequency generation vibrational spectroscopy. Although complex formation between highly charged surfactants and polyelectrolytes of the same charge is generally expected to be prohibited by the electrostatic repulsive force, our study shows that it is possible to form thermodynamically stable complexes when excess ions are present in the solution. We found that anionic partially hydrolyzed polyacrylamide (HPAM) could interact with anionic sodium dodecyl sulfate (SDS) on a water surface in the presence of salts. With excess Na+ ions in the solution, the charge screening effect allows HPAM to weakly interact with SDS via hydrogen bonds. In the presence of divalent Ca2+ ions, the surfactant and the polymer are strongly coupled by forming Ca2+ ion bridges and hydrogen bonds. Our calculation shows that the presence of Ca2+ ions creates a steep binding energy of similar to 30 kJ/mol near the water surface. These results were qualitatively verified using phase-sensitive sum-frequency generation vibrational spectroscopy.