In this study, we employed the Heck reaction method to synthesize three types of hybrid porous organic/inorganic polymers (HPPs) incorporating octavinylsilsesquioxane (OVS) units. Specifically, we synthesized OVS-TBN-DBTH, OVS-TBN-THS, and OVS-TBN-THSO2 HPPs by reacting OVS with different brominated organic compounds, namely, 2,7,10,15-tetrabromodibenzo[g,p]chrysene (TBN-Br4)/2,8-dibromodibenzo[b,d]thiophene (DBTH-Br2), TBN-Br4/2,3,7,8-tetrabromothianthrene (THS-Br4), and TBN-Br4/2,3,7,8-tetrabromothianthrene-5,5,10,10-tetraoxide (THSO2-Br4). Based on thermal analysis (TGA), the onset decomposition temperatures (Td10) for these HPPs were as follows: OVS-TBN-DBTH at 575 °C, OVS-TBN-THS at 313 °C, and OVS-TBN-THSO2 at 490 °C. Additionally, these HPPs exhibited high char yields, with values of 83, 53, and 67 wt% for OVS-TBN-DBTH, OVS-TBN-THS, and OVS-TBN-THSO2 HPPs, respectively. Furthermore, when analyzed using nitrogen adsorption–desorption measurements, both OVS-TBN-DBTH and OVS-TBN-THSO2 HPPs demonstrated impressive specific surface areas (SBET) of up to 380 m2/g. In addition, the OVS-TBN-DBTH and OVS-TBN-THSO2 HPPs provide an adsorption capacity of 70.62 and 77.1 mg g−1 (qmax from Langmuir isothermal Mode) toward RhB dyestuff at room temperature. In this adsorption system, after calculation, the OVS-TBN-THS HPP could be inferred that the adsorption is a pseudo-first order adsorption model. The OVS-TBN-THS HPP and OVS-TBN-THSO2 HPP in the pseudo-secondary order model have a better representation of the adsorption system for rhodamine B. This study introduces an innovative method for developing HPPs as adsorbents for water treatment and purification.