Porous coordination polymers or metal–organic frameworks have been proposed as promising catalyst materials since their discovery. A fundamental problem associated with MOF-based catalysts is the stability during their catalytic performance, especially in liquid-phase catalysis. Herein, we report on the controlled incorporation of nanoscale palladium and titanium dioxide inside MIL-101 (Cr). The introduction of the metal species was accomplished by metal-organic chemical vapor deposition and can be varied over a large weight-percentage range. The enhanced catalytic activity and the improved reusability of the resulting Pd/TiO2@MIL-101 composite materials were demonstrated in hydrogenation and dehydrogenation reactions. Furthermore, the presence of TiO2(amorphous) allowed observing an enhanced photocatalytic activity.