A novel alginate/poly(acrylic acid/acrylamide) double-network hydrogel composite with silver nanoparticles was successfully fabricated using the sol–gel method. The presence of carboxyl and amide groups in the network structure provided abundant active sites for complexing silver ions, facilitating the in situ reduction and confinement of silver nanoparticles. In batch experiments, the optimal silver loading was 20%, and 5 mmol·L–1 of p-nitrophenol was completely degraded in 113 s with a rate constant value of 4.057 × 10−2 s–1. In the tap water system and simulated seawater system, the degradation time of p-nitrophenol at the same concentration was 261 and 276 s, respectively, with a conversion rate above 99%. In the fixed-bed experiment, the conversion rate remained above 74% after 3 h at a flowing rate of 7 mL·min–1. After 8 cycling tests, the conversion rate remained at 98.7%. Moreover, the catalyst exhibited outstanding performance in the degradation experiment of four typical organic dyes.