Porous organic copolymer (designated as CPOL-BP&P(OPh)(3)) containing vinyl biphephos moieties and tris (4-vinylphenyl)phosphite (P(OPh)(3)) moieties was synthesized through a solvothermal copolymerization technique. After metalation with Rh precursor, an efficient heterogeneous catalyst Rh/CPOL-BP&P(OPh)(3) for the hydroformylation of 1-butene is presented with high activity (TOF = 2490.3 h(-1)) and regioselectivity (l:b = 40.0). The Rh/CPOL-BP&P(OPh)(3) catalyst has been investigated by using solid-state C-13 MAS NMR, in situ FT-IR spectroscopy, nitrogen sorption measurements, SEM, TEM, and XPS. Interestingly, in situ FT-IR spectra showed that Rh species tended to coordinate with both two kinds of P species from biphephos and P(OPh)(3) ligands in the Rh/CPOL-BP&P(OPh)(3) polymer frame rather than one kind of them. Therefore, the synergistic effect of three kinds of coordination compound formed between Rh species and both ligands could be responsible for the high activity and regioselectivity observed in hydroformylation of 1-butene. (C) 2018 Elsevier Inc. All rights reserved.