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A novel prototype based on the combination of a multi-junction, high-efficiency photovoltaic (PV) module and a supercapacitor (SC) able to self-power a wireless sensor node (WSN) for outdoor air quality monitoring has been developed and tested. A PV module with about an 8 cm2 active area made of eight GaAs-based triple-junction solar cells with a nominal 29% efficiency was assembled and characterized under terrestrial clear-sky conditions. Energy is stored in a 4000 F/4.2 V supercapacitor with high energy capacity and a virtually infinite lifetime (104 cycles). The node power consumption was tailored to the typical power consumption of miniaturized, low-consumption NDIR CO2 sensors relying on an LED as the IR source. The charge/discharge cycles of the supercapacitor connected to the triple-junction PV module were measured under illumination with a Sun Simulator device at selected radiation intensities and different node duty cycles. Tests of the miniaturized prototype in different illumination conditions outdoors were carried out. A model was developed from the test outcomes to predict the maximum number of sensor samplings and data transmissions tolerated by the node, thus optimizing the WSN operating conditions to ensure its self-powering for years of outdoor deployment. The results show the self-powering ability of the WSN node over different insolation periods throughout the year, demonstrating its operation for a virtually unlimited lifetime without the need for battery substitution.