A zirconia-based catalyst with controlled crystalline phases is synthesized through a simple thermal decomposition of a parent UiO-66 single precursor. The introduction of Ti(IV) and Hf(IV) cation into the Zr(IV) framework has been successfully obtained to tune the photocatalytic activity over methyl orange (MO) solution. Their resulting crystalline phases, morphologies, elemental analysis, band gap values, surface area, and photocatalytic degradation study over MO dye are presented and discussed. The tetragonal zirconia (t-ZrO2) catalyst exhibits the highest photocatalytic activity with 89% decoloration efficiency under UV irradiation (λ = 254 nm) for 300 min compared to m-ZrO2 (67%), the mixed phases (t-ZrO2 and m-ZrO2), as well as the synthesized mixed oxides ZrO2-MO2 (M = Ti or Hf), where the photocatalytic activities are 74% and 63%, respectively. This result is on par with commercially available anatase TiO2 and other reported t-ZrO2 catalysts.