The synthesis of phosphine-based functional covalent organic frameworks (COFs) has attracted great attention recently. Here, we present two examples of triphenylphosphine-based COFs (termed as P-COFs) with well-defined crystalline structures, high specific surface areas and good thermal stability. Furthermore, the rhodium catalysts using the obtained P-COFs as support materials show high turnover frequency (TOF) for the hydroformylation of olefins, as well as the excellent recycling performance. This work not only extended phosphine-based COFs family, but also demonstrated their application in immobilizing homogeneous metal-based (e.g., Rh- phosphine) catalysts for heterogeneous catalysis application.