We demonstrate the potential to tune the binding of calcium ions with polystyrene sulfonate (PSS) in the presence of dodecyl sulfate (DS). This can aid the design of surfactant-responsive water-softening agents for applications in detergency. We use molecular dynamics simulations to study the effect of the concentration of DS ions and the degree of sulfonation on the propensity of calcium ions toward PSS. We observe that the presence of DS ions increases the propensity of calcium ions toward 100% sulfonated PSS. The above phenomenon is due to the hydrophobic attraction between PSS and DS at low DS concentrations and the formation of calcium ion bridges between sulfonate and sulfate groups at moderate to high DS concentrations. We also observe the formation of calcium ion bridges between the sulfonate groups at high DS concentrations. The presence of DS ions also increases the propensity of calcium ions toward 20% sulfonated PSS. This is mainly due to the hydrophobic attraction between PSS and DS ions. The calcium ion bridges between sulfonate and sulfate groups are less prevalent than those of 100% sulfonated PSS. We do not observe calcium ion bridges between sulfonate groups of 20% sulfonated PSS. We use the above-mentioned insights to suggest potential strategies for designing an anionic polyelectrolyte having a suitable calcium-binding ability at a given concentration of the anionic surfactant. Finally, strong PSS-DS affinity is detrimental to the activity of surfactants because less surfactant ions are available for detergency. Our results also indicate the possibility of altering the PSS-DS affinity by changing the degree of sulfonation.