The new nanocomposites, Pd/C/ZrO2, PdO/ZrO2, and Pd/PdO/ZrO2, were prepared by thermal conversion of Pd@UiO‐66‐Zr−NH2 (MOF) in nitrogen or air atmosphere. The presence of Pd nanoparticles, uniformly distributed on the ZrO2 or C/ZrO2 matrix, was evidenced by transmission electron microscopy, scanning electron microscopy (SEM), Raman and X‐ray Photoelectron Spectroscopy (XPS) methods. All pyrolysed composites retained the shape of the MOF template. They catalyze carbonylative Suzuki coupling under 1 atm CO with an efficiency significantly higher than the original Pd@UiO‐66‐Zr−NH2. The most active PdO/ZrO2 composite, formed benzophenone with TOF up to 1600 h−1, while by using Pd@UiO‐66‐Zr−NH2, much lower TOF values, 51–95 h−1, were achieved. After the reaction, PdO/ZrO2 was recovered with the same composition and catalytic activity. Very good results were also obtained in the transfer hydrogenation of benzophenones to alcohols with Pd/C/ZrO2 and PdO/ZrO2 catalysts under microwave irradiation. New Pd/C/ZrO2 and PdO/ZrO2 nanocomposites, obtained by direct pyrolysis of Pd@UiO‐66‐NH2 under nitrogen or air, presented high ability to form benzophenone according to carbonylative Suzuki pathway under 1 atm of CO with TOF up to 1600 h−1. Pd/ZrO2 nanocomposites are superior catalysts of Suzuki–Miyaura and carbonylative Suzuki–Miyaura coupling than the original Pd@UiO‐66‐NH2. Its morphology was preserved during the catalytic reaction.