Urban climates are highly influenced by the ability of built surfaces to reflect solar radiation, and the use of high-albedo materials has been widely investigated as an effective option to mitigate urban overheating. While diffusely solar reflective walls have attracted concerns in the architectural and thermal comfort community, the potential of concave and polished surfaces, such as glass and metal panels, to cause extreme glare and localized thermal stress has been underinvestigated. Furthermore, there is the need for a systematic comparison of the solar concentration at the pedestrian level in front of tall buildings. Herein, we show the findings of an experimental campaign measuring the magnitude of the sunlight reflected by scale models reproducing archetypical tall buildings. Three 1:100 scaled prototypes with different shapes (classic vertical façade, 10% tilted façade, curved concave façade) and different finishing materials (representative of extremes in reflectance properties of building materials) were assessed. A specular surface was assumed as representative of a glazed façade under high-incidence solar angles, while selected light-diffusing materials were considered sufficient proxies for plaster finishing. With a diffusely reflective façade, the incident radiation at the pedestrian level in front of the building did not increase by more than 30% for any geometry. However, with a specular reflective (i.e., mirror-like) flat façade, the incident radiation at the pedestrian level increased by more than 100% and even by more than 300% with curved solar-concentrating geometries. In addition, a tool for the preliminary evaluation of the solar reflectance risk potential of a generic complex building shape is developed and presented. Our findings demonstrate that the solar concentration risk due to mirror-like surfaces in the built environment should be a primary concern in design and urban microclimatology.