The porous and water-stable polyoxometalates-based Zr-MOFs PW12@UiO-NH2 was proposed for photocatalytic H-2 evolution and degradation pollutants via adopting Keggin-type polyoxometalates (POMs) into UiO-66-NH2 through a facile one-step solvothermal method. Systematically characterizations were carried out to confirm the encapsulation of Keggin-type PW12 within the cavities of porous UiO-66-NH2 without modifying its fundamental framework. Benifiting from the integration of Keggin-type PW12 units with redox activity and porous UiO-66-NH2, the results showed that enhanced photocatalytic H-2 evolution performance and RhB degradation activity for PW12@UiO-NH2 were realized compared with pristine UiO-66-NH2 under visible-light irradiation. The significant improvement of photocurrent density under a monochromatic light irradiation implied the faciliated separation procedure of photo-generated charge carriers with the incorporation of Keggin-type PW12 units. Hence, our findings reveal a novel topology POM-based MOFs which paves a way for environmental and energy applications.