Adopting a cationic fluorescent molecule, rhodamine 6G, as the probe of the counterions of the model anionic polyelectrolyte (sodium polystyrene sulfonate, PSSNa), the diffusion of the counterion probes inside the solution of PSSNa was studied by fluorescence correlation spectroscopy. Two species of the counterion probes with different diffusion coefficient were discovered--the freely diffusing probes and the probes bound to the PSS(-) chains. The concentration fraction of these two species was found to change with the concentration and molecular weight of PSSNa. The results show that the counterion binding to the PSS(-) chain is enhanced with the increase of polymer concentration, attributed to the result of the lowered translational entropic penalty at higher polymer concentrations. The counterion binding is also enhanced with the increase of molecular weight, and the origin was attributed to the chain end effect to the counterion distribution. The results indicate the dynamic exchange process between the free counterions and the bound ones, which is further evidenced by the replacement of the bound probes by the elevated salt levels in the solution.