Synthesis of sulfonated porous polymers with improved hydrophobicity and stability is of extreme importance in both academic research and industrial applications. However, there is often a trade‐off between acidity and surface hydrophobicity of sulfonated polymers. In this study, we report a strategy for the synthesis of sulfonated porous organic polymers (S‐PT) with improved hydrophobicity via free radical polymerization method by using a rigid and large multidentate monomer, 1,3,5‐tri(4‐vinylphenyl)‐benzene, having a hydrophobic core. The results of vapor adsorption measurement show that S‐PT has more hydrophobic properties than sulfonated poly(divinylbenzene) (S‐PD), attributed to the hydrophobic core of its multidentate monomer. Furthermore, the optimization of sulfonation time established a balance between surface acidity and hydrophobicity. Under optimized conditions, S‐PT afforded up to 113 mmol g−1 h−1 TOF in the esterification of oleic acid with methanol, more active than commercial Amberlyst‐15 with TOF of 15 mmol g−1 h−1 and Nafion NR50 with TOF of 7 mmol g−1 h−1. We believe that the findings of this study will provide useful insights to advance the design and synthesis of solid acid catalysts for organic transformations.