A series of porous organic polymer (POP) supports were synthesized by simple Friedel-Crafts reactions using toluene, phenol, and hydroquinone as monomers. Pd nanoparticles were loaded onto the supports through impregnation and reduction, resulting in a series of porous organic polymer-supported Pd nano-catalysts with varying hydroxyl contents. The catalysts were characterized using FTIR, XRD, XPS, SEM, and TEM. The effect of surface hydroxyl groups on the catalytic dehydrogenative coupling reaction of silanes with alcohols was investigated. The results showed that the more surface hydroxyl groups on the catalyst, the stronger the interaction with Pd, leading to the best catalyst cycling stability (no significant changes in conversion and selectivity after 7 cycles). Furthermore, these catalysts exhibited excellent activity (conversion of dimethylphenylsilane >99%) and selectivity (selectivity of dimethylphenylethoxysilane >99%) in the catalytic dehydrogenative coupling reaction between dimethylphenylsilane with ethanol. Additionally, catalysts with hydroxyl groups were also suitable for the dehydrogenative coupling reactions of various silanes and alcohol substrates (targeted silyl ethers yields ranging from 34% to 99%).