The novel Pd‐nanocomposites, fabricated via calcination of the MOF Pd(2‐pymo)2n (2‐pymo=2‐pyrimidinolate), were used for the first time in the transfer hydrogenation of phenylacetylene with NaBH4. The presence of Pd NPs or PdO in the studied materials was evidenced by XPRD, Raman spectroscopy, XPS and HR‐TEM. Under mild reaction conditions, in water as a solvent, Pd‐nanocomposites, Pd/CPYMO and PdO/Pd/CPYMO, provided better catalytic results than the pristine Pd(2‐pymo)2n, producing styrene with good selectivity. These two catalysts showed also good durability in subsequent reuses, while the productivity of PdO/CPYMO decreased after the second run. Nanocomposites: MOFs‐templated strategy was used to fabricate palladium nanocatalysts for heterogeneous transfer hydrogenation of phenylacetylene with NaBH4 in water. Pd‐nanocomposites, fabricated via calcination of the Pd(2‐pymo)2n, presented high activity and selectivity towards styrene. The presence of Pd NPs or PdO in the studied materials was evidenced by XPRD, Raman spectroscopy, XPS and HR‐TEM. In all catalysts Pd0 was found after catalytic reaction.