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Harnessing energy from the sunlight using solar photovoltaic trees (SPVTs) has become popular at present as they reduce land footprint and offer numerous complimentary services that offset infrastructure. The SPVT’s complimentary services are noticeable in many ways, e.g., electric vehicle charging stations, landscaping, passenger shelters, onsite energy generated security poles, etc. Although the SPVT offers numerous benefits and services, its deployment is relatively slower due to the challenges it suffers. The most difficult challenges include the structure design, the photovoltaic (PV) cell technology selection for a leaf, and uncertainty in performance due to weather parameter variations. This paper aims to provide the most practical solution supported by the performance prioritization approach (PPA) framework for a typical multilayered SPVT. The proposed PPA framework considers the energy and sustainability indicators and helps in reporting the performance of a multilayered SPVT, with the aim of selecting an efficient PV leaf design. A three-layered SPVT (3-L SPVT) is simulated; moreover, the degradation-influenced lifetime energy performance and carbon dioxide (CO2) emissions were evaluated for three different PV-cell technologies, namely crystalline silicon (c-Si), copper indium gallium selenide (CIGS), and cadmium telluride (CdTe). While evaluating the performance of the 3-L SPVT, the power conversion efficiency, thermal regulation, degradation rate, and lifecycle carbon emissions were considered. The results of the 3-L SPVT were analyzed thoroughly, and it was found that in the early years, the c-Si PV leaves give better energy yields. However, when degradation and other influencing weather parameters were considered over its lifetime, the SPVT with c-Si leaves showed a lowered energy yield. Overall, the lifetime energy and CO2 emission results indicate that the CdTe PV leaf outperforms due to its lower degradation rate compared to c-Si and CIGS. On the other side, the benefits associated with CdTe cells, such as flexible and ultrathin glass structure as well as low-cost manufacturing, make them the best acceptable PV leaf for SPVT design. Through this investigation, we present the selection of suitable solar cell technology for a PV leaf.