Vinyl functionalized Biphephos ligand, denoted as vinyl biphephos, has been succesfully synthesized. Copolymerization of vinyl biphephos with tris(4-vinphenyl) phosphane can afford an efficient Porous Organic Polymer (POP), CPOL-bp&PPh₃. The ultimately formed Rh/CPOL-bp&PPh₃ heterogeneous catalyst showed excellent performance in converting terminal olefins to the corresponding linear aldehydes with high regioselectivity (l/b = 96 : 4–98 : 2), activity and stability, even better than the comparable homogeneous Rh + vinyl biphephos system. Notably, isomerizing hydrofromylation of internal olefins (2-heptene, 2-octene, trans-3-hexene) was also performed with high regioselectivity (l/b = 92 : 8–93 : 7) using the Rh/CPOL-bp&PPh₃ heterogeneous catalyst.