A novel hybrid network was synthesized in two steps: the first step involved the attachment of glycidyl methacrylate (GMA) to octa(aminophenyl) silsesquioxane (OAPS) through a ring-opening reaction, forming a hybrid dendrimer structure, and the second step involved the cross-linking of hybrid dendrimer using an azobisisobutyronitrile initiator to create the final hybrid network of OAPS-GMA. The synthesized hybrid material was comprehensively characterized using fourier transform infrared Spectroscopy (FTIR), nuclear magnetic resonance ((1H, 13C, and 29Si NMR) spectroscopy, thermogravimetric Analysis (TGA), and scanning electron microscopy (SEM). The BET surface area was found to be 25.44 m2/g, and significant 2.341 cm3/g of total pore volume was observed. The TGA analysis shows that the material is highly stable up to 450 °C. The synthesized network demonstrated remarkable adsorption capacities for iodine and dyes. It exhibited an iodine adsorption capacity of 3.4 g/g from vapors and 874 mg/g from solution. Additionally, it showed significant adsorption capacities for Rhodamine B and Congo red, with values of 762 mg/g and 517 mg/g, respectively. This study not only provides a novel method for preparing GMA-functionalized silsesquioxane-based porous hybrid polymers but also contributes to advancing solutions for environmental pollution issues.