Solar photothermo-catalysis is a fascinating multi-catalytic approach for volatile organic compounds (VOCs) removal. In this work, we have explored the performance and the chemico-physical features of non-critical, noble, metal-free MnOx-ZrO2 mixed oxides. The structural, morphological, and optical characterizations of these materials pointed to as a low amount of ZrO2 favoured a good interaction and the ionic exchange between the Mn and the Zr ions. This favoured the redox properties of MnOx increasing the mobility of its oxygens that can participate in the VOCs oxidation through a Mars-van Krevelen mechanism. The further application of solar irradiation sped up the oxidation reactions promoting the VOCs total oxidation to CO2. The MnOx-5 wt.%ZrO2 sample showed, in the photothermo-catalytic tests, a toluene T90 (temperature of 90% of conversion) of 180 °C and an ethanol T90 conversion to CO2 of 156 °C, 36 °C, and 205 °C lower compared to the thermocatalytic tests, respectively. Finally, the same sample exhibited 84% toluene conversion and the best selectivity to CO2 in the ethanol removal after 5 h of solar irradiation at room temperature, a photoactivity similar to the most employed TiO2-based materials. The as-synthetized mixed oxide is promising for an improved sustainability in both catalyst design and environmental applications.