Developing noble-metal-based catalysts with ultralow loading to achieve excellent performance for selective hydrogenation of alkynes under mild reaction conditions is highly desirable but still faces huge challenges. To this end, a SO3H-anchored covalent organic framework (COF-SO3H) as the support was deliberately designed, and then ultralow-content Pd (0.38 wt %) was loaded by a wet-chemistry immersion dispersion method. The resulting Pd-0.38/COF-SO3H composite exhibits outstanding performance for the selective hydrogenation of phenylacetylene with 97.06% conversion and 93.15% selectivity to styrene under mild reaction conditions (1 bar of H-2, 25 degrees C). Noticeably, the turnover frequency value reaches as high as 3888 h(-1), which outperforms most of reported catalysts for such use. Moreover, such a catalyst also exhibits excellent activity for a series of other alkynes and high stability without obvious loss of catalytic performance after five consecutive cycles.