Urban green infrastructure (UGI) and nature-based solutions (NBS) are increasingly recognized as strategies to address urban sustainability challenges. These solutions are attracting key scientific and marketing attention thanks to their capability to improve indoor and outdoor thermal comfort and environmental quality of spaces. In urban areas, where most of the population worldwide lives, indoor-outdoor environmental quality is compromised by local and temporary overheating phenomena, air pollution concentration, and impervious surfaces minimizing urban space resilience to climate change related hazards. In this view, the proposed study concerns the analysis of a greenery system for enhancing outdoor thermal conditions and local warming mitigation for pedestrians for the continental Mediterranean climate. The system has the purpose of designing an outdoor “alive” shading system to be applied in open public spaces, with producing physical and societal benefits. The experimental results showed that the implementation of the greenery, characterized by lower surface temperatures and evapotranspiration compared to a simple pergola system, allows the reduction of outdoor air temperature under the shading system and, thus, higher relative humidity in summer. Specifically, the hygrothermal cooling and the additional shading thanks to the presence of greenery provide local air temperature reduction up to 5 °C at pedestrian level.