The selectivity of the linear polymer chain toward its binding moieties has been considered negligible; thus, a clear demonstration showing the best-fit binding of a linear polymer to its guest counterpart is still unknown. Luminescent poly(acrylic acid) (PAA)-stabilized silver nanodots (PAA-AgNDs) have been applied as a turn-on sensor to monitor the interaction between the PAA chain and its binding cations. The binding of cations ions to the PAA chain may cross-link the linear PAA chain via coordination with carboxylate, which increases the rigidity of the polymer chain, retards the nonradiative decay of PAA-AgNDs, and consequently enhances the emission of silver nanodots while inducing a blue-shift of its emission spectrum. For the first time, we have demonstrated that a linear polymer chain can act as an open host to selectively bind to its best-matching cations. Specifically, among Group 2 cations (Mg2+, Ca2+, Sr2+, Ba2+), calcium ions show the strongest bonding to the PAA polymer chain. Our research suggests that, with extra rigidity, the polymer improves its chemical stability as calcium ions cross-linked the linear polymer. Meanwhile, it has also been demonstrated that luminescent silver nanodots can be excellent probes for the detection of polymer activities with straightforward and simple visualization methods.