The spatial correlation of counterions [Li+, Na+, Rb+, Cs+, NH4+, (CH3)(4)N+] with spherical polyelectrolyte brushes (SPBs), which consist of a PS core and chemically grafted PSS chains, was comprehensively studied through a combination of SAXS, DLS, and Zeta potential. Results show that the SAXS intensity profiles of the brush appears to be "insensitive" to the concentration of Na+. By contrast, introducing salt ions with a density lower than sodium [NH4+, (CH3)(4)N+ and Li+] into the brush layer will cause a decrease in the scattering intensity while introducing those with a higher density than sodium (Rb+ and Cs+) will cause the opposite result. As verified by the combined results of SAXS, DLS, and Zeta potential, the collapse of the brush and the enrichment of the counterions in the brush layer occur simultaneously. It was further demonstrated that the concentration of counterions enriched in the innermost layer of the brush shell can be enhanced up to hundreds of times compared with the bulk concentration, and the counterion distribution in SPB shell follows a radial attenuation distribution. SAXS is confirmed to be powerful in probing the enrichment and distribution of counterions within SPB. (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 738-747