A Pd-containing catalyst based on a layered substrate obtained by the polymerization of 2,3,6,7,10,11-hexahydroxytriphenylene and terephthalic aldehyde was developed and studied. The process of liquid-phase hydrogenation of phenylacetylene was studied on the obtained catalyst. It was found that high selectivity for styrene (97%) with complete phenylacetylene conversion is achieved at a hydrogen pressure of 0.1 MPa and a temperature of 40˚C. It has been shown that the catalyst exhibits high stability—maintaining conversion and selectivity for 6 cycles.