Poly(styrene sulfonic acid) (PSSA) hydrogel was prepared by radiation crosslinking using methyl N, N-bisacrylamide as crosslinker. Effects of ion species and concentration on the swelling behavior of PSSA hydrogel were investigated in aqueous solution of selected anions (F-, Cl-, Br-, SCN-), cations (Li+, Na+, K+, Ca2+), and hydrophobic ions (tetramethylammonium cation TMA(+), tetrabutylammonium cation TBA(+), and dodecyltrimethylammonium cation TAB(+)). The deswelling extent of PSSA hydrogel follows anion Hofmeister series, i.e., SCN- < Br- < Cl- < F-, in solutions containing selected anions and K+ as counterion up to a concentration of 2 mol, L-1. On the contrary, the deswelling extent of PSSA hydrogel in solutions containing selected cations and Cl-follows the sequence of Li+ < Na+ < K+ < Ca-2+,Ca- which is the reverse of the Hofmeister series except Ca2+. We have discussed the effects of ions on the hydrogen bonding through SO3- and phenyl ring in salt solutions at low and high concentrations. Other interactions, such as the cation-pi and hydrophobic interactions, also contributed to the ion-specific swelling of PSSA hydrogel. The proposed mechanism was further elucidated by FTIR and NMR analysis. A very specific deswelling-reswelling phenomenon of PSSA hydrogel in KF solution has been observed and ascribed to the F- binding to phenyl ring through a specific interaction.