Phosphine-containing porous organic polymers (phosphine-POPs) are a kind of potential catalyst support for alkene hydroformylation. However, the synthesis of phosphine-POPs with strong π-acceptor is still a challenge. Herein, we report the synthesis of phosphine-POPs with different π-acceptor properties [POL-P(Pyr) 3 , CPOL-BPa&PPh 3 -15, and CPOL-BP&PPh 3 -15] and evaluated their performances as ligands to coordinate with Rh(acac)(CO) 2 for hydroformylation of alkenes. We found that the Rh center with stronger π-acceptor phosphine-POPs showed better catalytic performance. Rh/CPOL-BPa&PPh 3 -15 with strong π-acceptor bidentate phosphoramidites showed obviously higher activity and regioselectivity (TON = 7.5 × 10 3 , l/b = 26.1) than Rh/CPOL-BP&PPh 3 -15 (TON = 5.3 × 10 3 , l/b = 5.0) with weaker π-acceptor bidentate phosphonites. Particularly, the TON of the hydroformylation reached 27.7 × 10 3 upon using Rh/POL-P(Pyr) 3 which possessed tris(1-pyrrolyl)phosphane coordination sites. Overall, our study provides an orientation to design phosphine-POPs for hydroformylation reactions.