Three new types of Si-centered porous organic polymer (Si-POPs) were successfully prepared using phenolic resin-type chemistry to form C-C bonds. This new family of microporous Si-POPs manifests as uniform, microporous, spherical particles with a high specific surface area. Notably, Si-POPs were engineered to possess varying numbers of hydroxyl (-OH) groups by altering the monomer in the synthetic process. Among these materials, the variant with the highest number of hydroxyl groups exhibited ultra-high CO