Polyelectrolyte complex (PEC) hydrogel, formed via physically electrostatic crosslinks between polyanion and polycation, is an interesting hydrogel in terms of its nontoxicity and solvent-free technique. In this work, poly (sodium 4-styrenesulfonate) (PSS)/poly (diallyl dimethyl ammonium chloride) (PDADMAC) complex hydrogels were prepared. Firstly, the PSS/PDADMAC complex aggregates using various PSS/PDADMAC mole fractions that were prepared in the presence of NaCl solution. Then, the aggregates were resolubilized under stirring at 70 °C for 2 h to obtain a homogeneous PEC solution. Finally, the PEC solution was dialyzed using a dialysis membrane with 3500 molecular cut-off for 1 day. The dialysis bath was changed every interval period of 2 h to control the rate of reversible electrostatic interaction, resulting in the homogenous PEC hydrogel with porous morphology as revealed by SEM and BET investigations. The dimensional stability and viscoelasticity of the PEC hydrogel was studied by DMA experiment, which showed the viscoelastic behavior at a compressive force ranging from 0 to 0.1 N. Finally, PSS/PDADMAC hydrogels showed a high water absorbency property and excellent affinity to textile anionic dyes.